EP3219683A1 - Zwischenfolie für verbundglas sowie verbundglas - Google Patents
Zwischenfolie für verbundglas sowie verbundglas Download PDFInfo
- Publication number
- EP3219683A1 EP3219683A1 EP15858216.3A EP15858216A EP3219683A1 EP 3219683 A1 EP3219683 A1 EP 3219683A1 EP 15858216 A EP15858216 A EP 15858216A EP 3219683 A1 EP3219683 A1 EP 3219683A1
- Authority
- EP
- European Patent Office
- Prior art keywords
- laminated glass
- layer
- interlayer film
- less
- mass
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Withdrawn
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2307/00—Properties of the layers or laminate
- B32B2307/70—Other properties
- B32B2307/732—Dimensional properties
- B32B2307/734—Dimensional stability
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2309/00—Parameters for the laminating or treatment process; Apparatus details
- B32B2309/08—Dimensions, e.g. volume
- B32B2309/10—Dimensions, e.g. volume linear, e.g. length, distance, width
- B32B2309/105—Thickness
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B25/00—Layered products comprising a layer of natural or synthetic rubber
- B32B25/04—Layered products comprising a layer of natural or synthetic rubber comprising rubber as the main or only constituent of a layer, which is next to another layer of the same or of a different material
- B32B25/042—Layered products comprising a layer of natural or synthetic rubber comprising rubber as the main or only constituent of a layer, which is next to another layer of the same or of a different material of natural rubber or synthetic rubber
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2605/00—Vehicles
- B32B2605/006—Transparent parts other than made from inorganic glass, e.g. polycarbonate glazings
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B60—VEHICLES IN GENERAL
- B60J—WINDOWS, WINDSCREENS, NON-FIXED ROOFS, DOORS, OR SIMILAR DEVICES FOR VEHICLES; REMOVABLE EXTERNAL PROTECTIVE COVERINGS SPECIALLY ADAPTED FOR VEHICLES
- B60J1/00—Windows; Windscreens; Accessories therefor
- B60J1/02—Windows; Windscreens; Accessories therefor arranged at the vehicle front, e.g. structure of the glazing, mounting of the glazing
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B60—VEHICLES IN GENERAL
- B60J—WINDOWS, WINDSCREENS, NON-FIXED ROOFS, DOORS, OR SIMILAR DEVICES FOR VEHICLES; REMOVABLE EXTERNAL PROTECTIVE COVERINGS SPECIALLY ADAPTED FOR VEHICLES
- B60J1/00—Windows; Windscreens; Accessories therefor
- B60J1/08—Windows; Windscreens; Accessories therefor arranged at vehicle sides
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B60—VEHICLES IN GENERAL
- B60J—WINDOWS, WINDSCREENS, NON-FIXED ROOFS, DOORS, OR SIMILAR DEVICES FOR VEHICLES; REMOVABLE EXTERNAL PROTECTIVE COVERINGS SPECIALLY ADAPTED FOR VEHICLES
- B60J1/00—Windows; Windscreens; Accessories therefor
- B60J1/18—Windows; Windscreens; Accessories therefor arranged at the vehicle rear
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B60—VEHICLES IN GENERAL
- B60J—WINDOWS, WINDSCREENS, NON-FIXED ROOFS, DOORS, OR SIMILAR DEVICES FOR VEHICLES; REMOVABLE EXTERNAL PROTECTIVE COVERINGS SPECIALLY ADAPTED FOR VEHICLES
- B60J7/00—Non-fixed roofs; Roofs with movable panels, e.g. rotary sunroofs
- B60J7/02—Non-fixed roofs; Roofs with movable panels, e.g. rotary sunroofs of sliding type, e.g. comprising guide shoes
- B60J7/04—Non-fixed roofs; Roofs with movable panels, e.g. rotary sunroofs of sliding type, e.g. comprising guide shoes with rigid plate-like element or elements, e.g. open roofs with harmonica-type folding rigid panels
- B60J7/043—Sunroofs e.g. sliding above the roof
Definitions
- the present invention relates to an interlayer film for laminated glass and a laminated glass.
- a method for producing a laminated glass having favorable sound insulating properties including forming an interlayer film having a three-layer structure by sandwiching a layer containing a copolymer of styrene and a rubber-based resin monomer between layers containing a thermally adhesive resin and laminating the interlayer film with two or more glasses (see, for example, PTL 3 or PTL 4) and a method for producing a laminated glass using a laminate having improved adhesiveness between layers by laminating a layer A containing a polyvinyl acetal and a layer B containing a polyolefin (see, for example, PTL 5) have been proposed.
- a conventional laminated glass has a problem that the sound insulating properties are deteriorated by reducing the thickness.
- a layer to be used in the interlayer film for the laminated glass may decrease the haze of the laminated glass or cause optical unevenness when producing the laminated glass in some cases.
- optical unevenness is likely to occur when a sound insulating interlayer film is embossed.
- Optical unevenness occurs at an interface between an inner layer and an outer layer of the interlayer film for laminated glass, and therefore, it is considered that the transfer of the shape to the inner layer when the interlayer film is embossed has an influence on the optical unevenness.
- examination of the embossing conditions or shaping of the surface by melt fracture is performed, however, the occurrence of optical unevenness cannot be sufficiently suppressed.
- the invention solves the above problems and has its object to provide an interlayer film for laminated glass which has excellent sound insulating properties even when the thickness is reduced, and also hardly causes optical unevenness and a laminated glass using the same.
- a limiting object of the invention is to provide an interlayer film for laminated glass which has excellent sound insulating properties even when the thickness is reduced, hardly causes optical unevenness, and also has excellent heat creep resistance.
- a laminated glass using an interlayer film for laminated glass having a specific structure has excellent sound insulating properties even when the thickness is reduced, and also hardly causes optical unevenness.
- an interlayer film for laminated glass and a laminated glass which have excellent sound insulating properties even when the thickness is reduced, and also hardly cause optical unevenness can be provided.
- the interlayer film for laminated glass of the invention includes at least one layer A containing a thermoplastic elastomer.
- the layer A is required to have a shear storage modulus at 70°C as measured by performing a dynamic viscoelasticity test at a frequency of 1,000 Hz in accordance with ASTM D4065-06 of a predetermined value or more.
- the layer A to be used in a laminate constituting the interlayer film for laminated glass of the invention contains a composition containing a specific thermoplastic elastomer.
- a specific thermoplastic elastomer By constituting the layer A by the composition containing a specific thermoplastic elastomer, the sound insulating properties of a laminate to be obtained can be improved.
- the thermoplastic elastomer refers to a polymer compound which is softened to exhibit plasticity when heated and is solidified to exhibit rubber elasticity when cooled, and is distinguished from a thermoplastic resin.
- thermoplastic elastomers such as a polystyrene-based elastomer (soft segment: polybutadiene, polyisoprene, or the like, hard segment: polystyrene), a polyolefin-based elastomer (soft segment: ethylene propylene rubber, hard segment: polypropylene), a polyvinyl chloride-based elastomer (soft segment: polyvinyl chloride, hard segment: polyvinyl chloride), a polyurethane-based elastomer (soft segment: polyether or polyester, hard segment: polyurethane), a polyester-based elastomer (soft segment: polyether, hard segment: polyester), a polyamide-based elastomer (soft segment: polypropylene glycol, polytetramethylene ether glycol, or polyester-based or polyether-based, hard segment: polyamide, hard segment: polyamide
- thermoplastic elastomer having at least one hard segment and at least one soft segment in the thermoplastic elastomer of the invention from the viewpoint of achieving both moldability and sound insulating properties also in a thin laminated glass due to favorable rubber elasticity. Further, from the viewpoint of further improving the sound insulating properties, it is more preferred to use a thermoplastic elastomer in which the hard segment block is a polystyrene block or a polymethyl methacrylate block.
- the content of the hard segment block in the thermoplastic elastomer is preferably 5 mass% or more, more preferably 10 mass% or more, further more preferably 12 mass% or more, particularly preferably 13 mass% or more, and most preferably 15 mass% or more.
- the content of the hard segment block in the thermoplastic elastomer is preferably 40 mass% or less, more preferably 30 mass% or less, and further more preferably 25 mass% or less.
- thermoplastic elastomer of the invention a rubber such as natural rubber, isoprene rubber, butadiene rubber, chloroprene rubber, nitrile rubber, butyl rubber, ethylene propylene rubber, urethane rubber, silicone rubber, chlorosulfonated polyethylene rubber, acrylic rubber, or fluororubber may be used.
- a rubber such as natural rubber, isoprene rubber, butadiene rubber, chloroprene rubber, nitrile rubber, butyl rubber, ethylene propylene rubber, urethane rubber, silicone rubber, chlorosulfonated polyethylene rubber, acrylic rubber, or fluororubber may be used.
- thermoplastic elastomer in the invention is a block copolymer having a hard segment block such as an aromatic vinyl polymer block (hereinafter sometimes referred to as “polymer block (a)”) and a soft segment block such as an aliphatic unsaturated hydrocarbon polymer block (hereinafter sometimes referred to as “polymer block (b)”), for example, a polystyrene-based elastomer.
- a aromatic vinyl polymer block
- polymer block (b) aliphatic unsaturated hydrocarbon polymer block
- the bonding form of these polymer blocks is not particularly limited, and may be any of linear, branched, and radial bonding forms, or a bonding form in which two or more of these bonding forms are combined, but is preferably a linear bonding form.
- linear bonding form examples include, when the aromatic vinyl polymer block is represented by "a” and the aliphatic unsaturated hydrocarbon polymer block is represented by “b”, a diblock copolymer represented by “a-b”, a triblock copolymer represented by “a-b-a” or “b-a-b”, a tetrablock copolymer represented by "a-b-a-b”, a pentablock copolymer represented by "a-b-a-b-a” or "b-a-b-a-b”, an (a-b)nX-type copolymer (X represents a coupling residue, and n represents an integer of 2 or more), and a mixture of these.
- a diblock copolymer or a triblock copolymer is preferred, and as the triblock copolymer, a triblock copolymer represented by "a-b-a” is more preferred.
- the total amount of the aromatic vinyl monomer unit and the aliphatic unsaturated hydrocarbon monomer unit in the block copolymer is preferably 80 mass% or more, more preferably 95 mass% or more, and further more preferably 98 mass% or more with respect to the total monomer units.
- the aliphatic unsaturated hydrocarbon polymer block in the block copolymer may be partially or completely hydrogenated.
- the content of the aromatic vinyl monomer unit in the block copolymer is preferably 5 mass% or more, more preferably 10 mass% or more, further more preferably 12 mass% or more, particularly preferably 13 mass% or more, and most preferably 15 mass% or more with respect to the total monomer units in the block copolymer.
- the content of the aromatic vinyl monomer unit in the block copolymer can be obtained from the charging ratio of the respective monomers when synthesizing the block copolymer and the measurement result of 1 H-NMR of the block copolymer, or the like.
- the content of the aromatic vinyl monomer unit in the block copolymer is preferably 40 mass% or less, more preferably 30 mass% or less, and further more preferably 25 mass% or less with respect to the total monomer units in the block copolymer.
- the content of the aromatic vinyl monomer unit in the block copolymer can be obtained from the charging ratio of the respective monomers when synthesizing the block copolymer and the measurement result of 1 H-NMR of the block copolymer, or the like.
- a monomer other than the aromatic vinyl monomer may be copolymerized if the amount is small.
- the ratio of the aromatic vinyl monomer unit in the aromatic vinyl polymer block is preferably 80 mass% or more, more preferably 95 mass% or more, and further more preferably 98 mass% or more with respect to the total monomer units in the aromatic vinyl polymer block.
- aromatic vinyl monomer constituting the aromatic vinyl polymer block examples include styrene; alkylstyrene such as ⁇ -methylstyrene, 2-methylstyrene, 3-methylstyrene, 4-methylstyrene, 4-propylstyrene, 4-cyclohexylstyrene, and 4-dodecylstyrene; arylstyrene such as 2-ethyl-4-benzylstyrene, 4-(phenylbutyl)styrene, 1-vinylnaphthalene, and 2-vinylnaphthalene; halogenated styrene; alkoxystyrene; and vinyl benzoate. These may be used alone or two or more types may be used in combination.
- a monomer other than the aromatic vinyl monomer may be copolymerized if the amount is small.
- the monomer other than the aromatic vinyl monomer include unsaturated monomers such as ethylene, propylene, 1-butene, 1-pentene, 1-hexene, 1-heptene, 1-octene, 1-nonene, 1-decene, 4-phenyl-1-butene, 6-phenyl-1-hexene, 3-methyl-1-butene, 4-methyl-1-butene, 3-methyl-1-pentene, 4-methyl-1-pentene, 3-methyl-1-hexene, 4-methyl-1-hexene, 5-methyl-1-hexene, 3,3-dimethyl-1-pentene, 3,4-dimethyl-1-pentene, 4,4-dimethyl-1-pentene, vinylcyclohexane, hexafluoropropene, tetrafluoroethylene, 2-fluoropropene, flu
- the content of the aliphatic unsaturated hydrocarbon monomer unit in the block copolymer is preferably 60 mass% or more, more preferably 70 mass% or more, and further more preferably 80 mass% or more with respect to the total monomer units in the block copolymer.
- the content of the aliphatic unsaturated hydrocarbon monomer unit in the block copolymer is less than 60 mass%, the characteristics as the thermoplastic elastomer tend to be difficult to exhibit.
- the content of the aliphatic unsaturated hydrocarbon monomer unit in the block copolymer is preferably 95 mass% or less, more preferably 90 mass% or less, and further more preferably 88 mass% or less with respect to the total monomer units in the block copolymer.
- the content of the aliphatic unsaturated hydrocarbon monomer unit in the block copolymer can be obtained from the measurement result of 1 H-NMR of the block copolymer, or the like.
- a monomer other than the aliphatic unsaturated hydrocarbon monomer may be copolymerized if the amount is small.
- the ratio of the aliphatic unsaturated hydrocarbon monomer unit in the aliphatic unsaturated hydrocarbon polymer block is preferably 80 mass% or more, more preferably 95 mass% or more, and further more preferably 98 mass% or more with respect to the total monomer units in the aliphatic unsaturated hydrocarbon polymer block.
- the aliphatic saturated hydrocarbon monomer in the aliphatic unsaturated hydrocarbon polymer block it is preferred to use a conjugated diene monomer.
- the type of the conjugated diene monomer is not particularly limited, however, examples thereof include butadiene, 1,3-pentadiene, 1,3-hexadiene, isoprene, cyclopentadiene, 1,3-cyclohexadiene, 1,3-octadiene, and 1,3-cyclooctadiene.
- These conjugated diene monomers may be used alone or two or more types may be used in combination.
- butadiene and isoprene in combination.
- the content of the conjugated diene in the polymer block is preferably 60 mass% or more, more preferably 70 mass% or more, further more preferably 80 mass% or more, and particularly preferably 90 mass% or more.
- the ratio of the conjugated diene monomer unit is within the above range, it is easy to exhibit the characteristics as the thermoplastic elastomer such as rubber elasticity, and thus, the sound insulating properties tend to be improved.
- Examples of the monomer other than the conjugated diene monomer as the aliphatic saturated hydrocarbon monomer in the aliphatic unsaturated hydrocarbon polymer block include unsaturated monomers such as ethylene, propylene, 1-butene, 1-pentene, 1-hexene, 1-heptene, 1-octene, 1-nonene, 1-decene, 4-phenyl-1-butene, 6-phenyl-1-hexene, 3-methyl-1-butene, 4-methyl-1-butene, 3-methyl-1-pentene, 4-methyl-1-pentene, 3-methyl-1-hexene, 4-methyl-1-hexene, 5-methyl-1-hexene, 3,3-dimethyl-1-pentene, 3,4-dimethyl-1-pentene, 4,4-dimethyl-1-pentene, vinylcyclohexane, hexafluoropropene, tetrafluoroethylene, 2-fluoropropene, fluoroethylene, 1,1
- the above aliphatic unsaturated hydrocarbon monomer is preferably a conjugated diene.
- a conjugated diene is used as the monomer constituting the aliphatic unsaturated hydrocarbon polymer block
- the amount of residual carbon-carbon double bonds derived from the conjugated diene monomer unit is preferably 2 mol% or more, more preferably 3 mol% or more, further more preferably 4 mol% or more, and particularly preferably 5 mol% or more.
- the amount of residual carbon-carbon double bonds derived from the conjugated diene monomer is preferably 40 mol% or less, more preferably 35 mol% or less, further more preferably 30 mol% or less, and particularly preferably 25 mol% or less.
- the weight average molecular weight of the block copolymer is preferably 30,000 or more, and more preferably 50,000 or more. Further, the weight average molecular weight of the block copolymer is preferably 400,000 or less, and more preferably 300,000 or less.
- the ratio of the weight average molecular weight to the number average molecular weight (Mw/Mn) of the block copolymer is preferably 1.0 or more. Further, the ratio of the weight average molecular weight to the number average molecular weight (Mw/Mn) of the block copolymer is preferably 2.0 or less, and more preferably 1.5 or less.
- the weight average molecular weight is a weight average molecular weight in terms of polystyrene determined by gel permeation chromatography (GPC) measurement, and the number average molecular weight is a number average molecular weight in terms of polystyrene determined by GPC measurement.
- a production method for the block copolymer is not particularly limited, however, the block copolymer can be produced by, for example, an anionic polymerization method, a cationic polymerization method, a radical polymerization method, or the like.
- an anionic polymerization method for example, an anionic polymerization method, a cationic polymerization method, a radical polymerization method, or the like.
- specific examples of the method include:
- thermoplastic elastomer In the case where a conjugated diene is used as the aliphatic unsaturated hydrocarbon monomer, by adding an organic Lewis base in the anionic polymerization, the amount of 1,2-bonds and the amount of 3, 4-bonds in the thermoplastic elastomer can be increased, and therefore, the amount of 1,2-bonds and the amount of 3,4-bonds in the thermoplastic elastomer can be easily controlled by the addition amount of the organic Lewis base.
- organic Lewis base examples include esters such as ethyl acetate; amines such as triethylamine, N,N,N',N'-tetramethylethylenediamine (TMEDA), and N-methylmorpholine; nitrogen-containing heterocyclic aromatic compounds such as pyridine; amides such as dimethyl acetamide; ethers such as dimethyl ether, diethyl ether, tetrahydrofuran (THF), and dioxane; glycol ethers such as ethylene glycol dimethyl ether and diethylene glycol dimethyl ether; sulfoxides such as dimethyl sulfoxide; and ketones such as acetone and methyl ethyl ketone.
- esters such as ethyl acetate
- amines such as triethylamine, N,N,N',N'-tetramethylethylenediamine (TMEDA), and N-methylmorpholine
- nitrogen-containing heterocyclic aromatic compounds such as
- the obtained unhydrogenated polystyrene-based elastomer is dissolved in a solvent inert to a hydrogenation catalyst, or the unhydrogenated polystyrene-based elastomer is used as it is without being isolated from the reaction mixture, and is reacted with hydrogen in the presence of a hydrogenation catalyst, whereby the hydrogenation can be carried out.
- the hydrogenation catalyst examples include Raney nickel; a heterogeneous catalyst obtained by supporting a metal such as Pt, Pd, Ru, Rh, or Ni on a carrier such as carbon, alumina, or diatomaceous earth; a Ziegler catalyst composed of a transition metal compound and an alkyl aluminum compound, an alkyl lithium compound, or the like in combination; and a metallocene-based catalyst.
- the hydrogenation reaction can "be generally performed under the conditions that the hydrogen pressure is 0.1 MPa or more and 20 MPa or less, the reaction temperature is 20°C or higher and 250°C or lower, and the reaction time is 0.1 hours or more and 100 hours or less.
- the thickness of the layer A is preferably 20 ⁇ m or more, more preferably 30 ⁇ m or more, and further more preferably 50 ⁇ m or more. When the thickness of the layer A is less than 20 ⁇ m, the sound insulating properties tend to be deteriorated. In the case where a plurality of layers A are included in the laminate constituting the interlayer film for laminated glass of the invention, it is preferred that the total thickness of the layers A satisfies the above conditions.
- the thickness of the layer A is preferably 400 ⁇ m or less, more preferably 250 ⁇ m or less, and further more preferably 200 ⁇ m or less.
- the thickness of the layer A exceeds 400 ⁇ m, in the case where a laminated glass is formed, the mechanical characteristics such as penetration resistance are deteriorated, and thus, the safety performance as a laminated glass tends to be impaired.
- a resin other than the above-mentioned elastomer or any of various additives such as a heat shielding material (for example, inorganic heat shielding fine particles or an organic heat shielding material having an infrared absorbing ability), an antioxidant, a UV absorber, a light stabilizer, an adhesive strength adjusting agent, a blocking inhibitor, a pigment, and a dye may be added as needed.
- a heat shielding material for example, inorganic heat shielding fine particles or an organic heat shielding material having an infrared absorbing ability
- an antioxidant for example, a UV absorber, a light stabilizer, an adhesive strength adjusting agent, a blocking inhibitor, a pigment, and a dye
- the heat shielding material may be contained in any of the layer A, and the below-mentioned layer B and layer C, and may be contained in only one of these layers or may be contained in a plurality of layers. In the case where the heat shielding material is contained, from the viewpoint of suppressing optical unevenness, the heat shielding material is preferably contained in at least one layer A.
- heat shielding material examples include tin-doped indium oxide (ITO), antimony-doped tin oxide (ATO), aluminum-doped zinc oxide (AZO), a phthalocyanine compound (NIOBP), a naphthalocyanine compound, a compound having an anthracyanine skeleton, metal-doped tungsten oxide represented by the general formula: M m WO n (M represents a metal element, and m is 0.01 or more and 1.0 or less, and n is 2.2 or more and 3.0 or less), zinc antimonate (ZnSb 2 O 5 ), and lanthanum hexaboride.
- ITO tin-doped indium oxide
- ATO antimony-doped tin oxide
- AZO aluminum-doped zinc oxide
- NIOBP a phthalocyanine compound
- naphthalocyanine compound a compound having an anthracyanine skeleton
- ITO, ATO, and metal-doped tungsten oxide are preferred from the viewpoint of infrared absorbability, and metal-doped tungsten oxide is particularly preferred.
- the metal element represented by M in the metal-doped tungsten oxide include Cs, Tl, Rb, Na, and K, and in particular, CWO (cesium-doped tungsten oxide) constituted by Cs is preferred.
- the above m is preferably 0.2 or more, and more preferably 0.3 or more. Further, the above m is preferably 0.5 or less, and more preferably 0.4 or less.
- the phthalocyanine compound is preferably a compound coordinated with nickel (II).
- the infrared absorbing ability of the heat shielding material is proportional to the optical path length (m) when infrared light passes through the layer A and the concentration (g/m 3 ) of the heat shielding material in the layer A. Therefore, the infrared absorbing ability of the heat shielding material is proportional to the area density (g/m 2 ) of the heat shielding material in the layer A.
- the area density (g/m 2 ) of the heat shielding material is preferably 0.10 or more, more preferably 0.15 or more, and further more preferably 0.20 or more.
- the area density (g/m 2 ) of the heat shielding material in the layer A is less than 0.10, a sufficient heat shielding effect tends to be difficult to obtain.
- the area density (g/m 2 ) of the heat shielding material is preferably 1.00 or less, more preferably 0.70 or less, and further more preferably 0.50 or less.
- the area density (g/m 2 ) of the heat shielding material in the layer A exceeds 1.00, in the case where a laminated glass is formed, the visible light transmittance tends to be decreased, the haze tends to be deteriorated, the weather resistance tends to be decreased, or the change in color difference tends to be increased.
- the area density (g/m 2 ) of the heat shielding material is preferably 0.50 or more, more preferably 1.00 or more, further more preferably 1.50 or more, particularly preferably 2.25 or more, and most preferably 3.00 or more.
- the area density (g/m 2 ) of the heat shielding material is preferably 15.00 or less, more preferably 10.50 or less, and further more preferably 7.50 or less.
- the area density (g/m 2 ) of the heat shielding material is preferably 1.00 or more, more preferably 1. 50 or more, and further more preferably 2.00 or more.
- the area density (g/m 2 ) of the heat shielding material is preferably 10.00 or less, more preferably 7.00 or less, and further more preferably 5.00 or less.
- the area density (g/m 2 ) of the heat shielding material is preferably 0.010 or more, more preferably 0.015 or more, and further more preferably 0.020 or more.
- the area density (g/m 2 ) of the heat shielding material is preferably 0.100 or less, more preferably 0.070 or less, and further more preferably 0.050 or less.
- the area density (g/m 2 ) of the heat shielding material is preferably 1.00 or more, more preferably 1.50 or more, and further more preferably 2.00 or more.
- the area density (g/m 2 ) of the heat shielding material is preferably 10.00 or less, more preferably 7.00 or less, and further more preferably 5.00 or less.
- the area density (g/m 2 ) of the heat shielding material is preferably 1.00 or more, more preferably 1.50 or more, and further more preferably 2.00 or more. In the case where zinc antimonate is used as the heat shielding material in the layer A, the area density (g/m 2 ) of the heat shielding material is preferably 10.00 or less, more preferably 7.00 or less, and further more preferably 5.00 or less.
- the area density (g/m 2 ) of the heat shielding material is preferably 0.02 or more, more preferably 0.03 or more, and further more preferably 0.04 or more.
- the area density (g/m 2 ) of the heat shielding material is preferably 0.20 or less, more preferably 0.14 or less, and further more preferably 0.10 or less.
- the heat shielding material may be contained in at least one layer of the layer A constituting the interlayer film for laminated glass, a layer having a higher shear storage modulus than the layer A, and a layer B, a layer C, or the like which may be included as needed. Above all, it is preferred that the heat shielding material is contained in at least the layer A. Further, in such a case, it is preferred that a UV absorber is contained in at least one layer, and it is more preferred that at least one type of UV absorber is contained in the layer B.
- the thermoplastic elastomer in the layer A is protected from UV light, and also the heat shielding properties of the interlayer film for laminated glass can be enhanced, and also the optical unevenness can be suppressed.
- the UV absorber which can be used in the invention is not particularly limited, however, examples thereof include benzotriazole-based UV absorbers such as 2-(5-chloro-2-benzotriazolyl)-6-tert-butyl-p-cresol, 2-(5-methyl-2-hydroxyphenyl)benzotriazole, 2-[2-hydroxy-3,5-bis( ⁇ , ⁇ '-dimethylbenzyl)phenyl]-2H-benzot riazole, 2-(3,5-di-t-butyl-2-hydroxyphenyl)benzotriazole, 2-(3-t-butyl-5-methyl-2-hydroxyphenyl)-5-chlorobenzotriazo le, 2-(3,5-di-t-butyl-5-methyl-2-hydroxyphenyl)-5-chlorobenzot riazole, 2-(3,5-di-t-amyl-2-hydroxyphenyl)benzotriazole, and 2-(2'-hydroxy-5'-t-octy
- triazine-based compound examples include 6-(4-hydroxy-3,5-di-t-butylanilino)-2,4-bis-octylthio-1,3, 5-triazine, 6-(4-hydroxy-3,5-dimethylanilino)-2,4-bis-octylthio-1,3,5-triazine, 6-(4-hydroxy-3-methyl-5-t-butylanilino)-2,4-bis-octylthio-1,3,5-triazine, and 2-octylthio-4,6-bis-(3,5-di-t-butyl-4-oxyanilino)-1,3,5-tr iazine.
- the triazine-based compound is regarded as falling under the category of a UV absorber and is not regarded as falling under the category of an antioxidant.
- benzophenone-based compound examples include 2-hydroxy-4-methoxybenzophenone, 2,2'-dihydroxy-4-methoxybenzophenone, 2-hydroxy-4-methoxy-2-carboxybenzophenone, and 2-hydroxy-4-n-octoxybenzophenone.
- malonic ester compound examples include dimethyl 2-(p-methoxybenzylidene)malonate, tetraethyl-2,2-(1,4-phenylenedimethylidene)bismalonate, and 2-(p-methoxybenzylidene)-bis(1,2,2,6,6-pentamethyl-4-piper idinyl)malonate.
- Examples of a commercially available product of the malonic ester compound include Hostavin B-CAP, Hostavin PR-25, and Hostavin PR-31 (all are manufactured by Clariant, Inc.).
- oxalic anilide compound examples include oxalic diamides having an aryl group or the like substituted on a nitrogen atom such as N-(2-ethylphenyl)-N'-(2-ethoxy-5-t-butylphenyl)oxalic diamide, N-(2-ethylphenyl)-N'-(2-ethoxy-phenyl)oxalic diamide, and 2-ethyl-2'-ethoxy-oxyanilide ("Sanduvor VSU" manufactured by Clariant, Inc.).
- oxalic diamides having an aryl group or the like substituted on a nitrogen atom such as N-(2-ethylphenyl)-N'-(2-ethoxy-5-t-butylphenyl)oxalic diamide, N-(2-ethylphenyl)-N'-(2-ethoxy-phenyl)oxalic diamide, and 2-ethyl-2'-
- the area density (g/m 2 ) of the UV absorber in the layer A is preferably 0.1 or more, more preferably 0.2 or more, and further more preferably 0.5 or more.
- the area density (g/m 2 ) of the UV absorber in the layer A is 0.1 or more, in the case where a laminated glass is formed, the haze tends to be improved, the weather resistance tends to be maintained, or the change in color difference tends to be suppressed.
- the area density (g/m 2 ) of the UV absorber in the layer A is preferably 10 or less, more preferably 9 or less, and further more preferably 8 or less.
- the area density (g/m 2 ) of the UV absorber in the layer A exceeds 10, in the case where a laminated glass is formed, the visible light transmittance tends to be decreased, the haze tends to be deteriorated, the weather resistance tends to be decreased, or the change in color difference tends to be increased.
- the addition amount of the UV absorber is preferably 10 ppm or more, and more preferably 100 ppm or more on a mass basis with respect to the resin contained in the layer A.
- the addition amount is less than 10 ppm, it is sometimes difficult to exhibit a sufficient effect.
- the addition amount of the UV absorber is preferably 50,000 ppm or less, and more preferably 10,000 ppm or less on a mass basis with respect to the resin contained in the layer A. Even if the addition amount is set to more than 50,000 ppm, a marked effect cannot be expected.
- antioxidants examples include a phenolic antioxidant, a phosphorus-based antioxidant, and a sulfur-based antioxidant.
- a phenolic antioxidant is preferred, and an alkyl-substituted phenolic antioxidant is particularly preferred.
- phenolic antioxidant examples include acrylate-based compounds such as 2-t-butyl-6-(3-t-butyl-2-hydroxy-5-methylbenzyl)-4-methylp henylacrylate, and 2,4-di-t-amyl-6-(1-(3,5-di-t-amyl-2-hydroxyphenyl)ethyl)ph enylacrylate; and alkyl-substituted phenolic compounds such as 2,6-di-t-butyl-4-methylphenol, 2,6-di-t-butyl-4-ethylphenol, octadecyl-3-(3,5-)di-t-butyl-4-hydroxyphenyl)propionate, 2,2'-methylene-bis(4-methyl-6-t-butylphenol), 4,4'-butylidene-bis(4-methyl-6-t-butylphenol), 4,4'-butylidene-bis(6-t-butyl-m
- Examples of the phosphorus-based antioxidant include monophosphite-based compounds such as tris(2,4-di-t-butylphenyl)phosphate, triphenylphosphite, diphenylisodecylphosphite, phenyldiisodecylphosphite, tris(nonylphenyl)phosphite, tris(dinonylphenyl)phosphite, tris(2-t-butyl-4-methylphenyl)phosphite, tris(cyclohexylphenyl)phosphite, 2,2-methylenebis(4,6-di-t-butylphenyl)octylphosphite, 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide, 10-(3,5-di-t-butyl-4-hydroxybenzyl)-9,10-dihydro-9-oxa-10-
- sulfur-based antioxidant examples include dilauryl 3,3'-thiodipropionate, distearyl 3,3-thiodipropionate, laurylstearyl 3,3'-thiodipropionate, pentaerythritol-tetrakis-( ⁇ -lauryl-thiopropionate), and 3,9-bis(2-dodecylthioethyl)-2,4,8,10-tetraoxaspiro[5.5]und ecane.
- the antioxidants can be used alone or two or more types can be used in combination.
- the area density of the antioxidant in the layer A is preferably 0.1 g/m 2 or more, more preferably 0.2 g/m 2 or more, and further more preferably 0.5 g/m 2 or more.
- the area density of the antioxidant in the layer A is less than 0.1 g/m 2 , the layer A is easily oxidized, and in the case where the laminated glass is used for a long period of time, the change in color difference is increased, and so on, and thus, the weather resistance tends to be decreased.
- the area density of the antioxidant in the layer A is preferably 2.5 g/m 2 or less, more preferably 1.5 g/m 2 or less, and further more preferably 2.0 g/m 2 or less.
- the area density of the antioxidant in the layer A exceeds 2.5 g/m 2 , the color tone of the layer A tends to be impaired or the haze of the laminated glass tends to be decreased.
- the blending amount of the antioxidant is preferably 0.001 parts by mass or more, and more preferably 0.01 parts by mass or more with respect to 100 parts by mass of the thermoplastic elastomer.
- amount of the antioxidant is less than 0.001 parts by mass, it is sometimes difficult to exhibit a sufficient effect.
- the blending amount of the antioxidant is preferably 5 parts by mass or less, more preferably 4 parts by mass or less, and further more preferably 3 parts by mass or less with respect to 100 parts by mass of the thermoplastic elastomer. Even if the amount of the antioxidant is set to more than 5 parts by mass, a marked effect cannot be expected.
- the light stabilizer examples include a hindered amine-based light stabilizer, for example, "ADEKA STAB LA-57 (trade name)” manufactured by ADEKA Corporation and “Tinuvin 622SF (trade name) " manufactured by Ciba Specialty Chemicals, Inc.
- the blending amount of the light stabilizer is preferably 0.01 parts by mass or more, and more preferably 0.05 parts by mass or more with respect to 100 parts by mass of the thermoplastic resin such as a polyvinyl acetal resin. When the amount of the light stabilizer is less than 0.01 parts by mass, it is sometimes difficult to exhibit a sufficient effect. Further, the content of the light stabilizer is preferably 10 parts by mass or less, and more preferably 5 parts by mass or less.
- the area density of the light stabilizer in the layer B is preferably 0.05 g/m 2 or more, and more preferably 0.5 g/m 2 or more. Further, the area density is preferably 70 g/m 2 or less, and more preferably 30 g/m 2 or less.
- an adhesive strength adjusting agent may be added to the layer A or the layer having a higher shear storage modulus than the layer A.
- the adhesive strength adjusting agent include polyolefins having an adhesive functional group such as a carboxyl group, a carboxyl group derivative group, an epoxy group, a boronic acid group, a boronic acid group derivative group, an alkoxyl group, or an alkoxyl group derivative group.
- the layer B is used as the layer having a higher shear storage modulus than the layer A, and a polyvinyl acetal resin is used in the layer B
- a polyolefin having an adhesive functional group is added to the layer A and performing coextrusion molding of the layer A and the layer B
- the addition amount of the polyolefin having an adhesive functional group is preferably 20 parts by mass or less, more preferably 15 parts by mass or less, and further more preferably 10 parts by mass or less with respect to 100 parts by mass of the thermoplastic elastomer in the layer A.
- the addition amount of the polyolefin having an adhesive functional group exceeds 20 parts by mass, in the case where a laminated glass is formed, the haze is sometimes deteriorated.
- polypropylene containing a carboxyl group is preferred among the above-mentioned polyolefins from the viewpoint of ease of availability, ease of adjustment of the adhesiveness, and ease of adjustment of the haze.
- the amount of the thermoplastic elastomer component in the composition containing the thermoplastic elastomer constituting the layer A is preferably 60 mass% or more, more preferably 70 mass% or more, further more preferably 80 mass% or more, particularly preferably 90 mass% or more, and most preferably 95 mass% or more.
- the amount of the thermoplastic elastomer in the layer A is less than 60 mass%, the characteristics as the thermoplastic elastomer tend to be difficult to exhibit or the optical characteristics tend to be impaired.
- the thermoplastic elastomer is contained in the laminate in an amount of preferably 5 mass% or more, more preferably 10 mass% or more, and further more preferably 13 mass% or more.
- the amount of the thermoplastic elastomer in the laminate is less than 5 mass%, the sound insulating properties tend to be deteriorated.
- the dynamic viscoelasticity of the interlayer film for laminated glass is defined in ASTM D4065-06, and can be measured with, for example, a mechanical spectrometer (model: DMA/SDTA861e, manufactured by Mettler Toledo, Inc.). The measurement can be performed by a fixed sinusoidal shear oscillation at a frequency of 1,000 Hz with a maximum shear strain amplitude of 0.1%.
- a test sample cut out from a polymer sheet obtained by compression molding a sample having a cylindrical shape with a thickness of 0.5 to 1.5 mm and a diameter of 3 to 5 mm can be used. The measurement can be performed in the range of -20 to 60°C at a temperature rising rate of 1°C/min.
- a shear storage modulus (G') and a shear loss modulus (G") can be obtained directly from the measurement.
- a "tan ⁇ " to be used as an index of the damping properties of a polymer and a shear complex modulus (G*) to be used as an index of the dynamic shear stiffness of a polymer can be obtained from the above G' and G" as defined in ASTM D4065-07.
- the sensitivity of hearing in human beings is high in the frequency range of 1,000 to 5, 000 Hz, and therefore, a tan ⁇ and a shear modulus at 20°C and 1,000 Hz can be used as the indices for determining the sound insulating properties of a polymer.
- the interlayer film for laminated glass having a high tan ⁇ value and a low shear modulus is preferred from the viewpoint of high sound insulating properties and high damping properties.
- the exemplary measurement result of tan ⁇ 11 of the layer A and the exemplary measurement result of shear complex modulus G* 12 of the layer A obtained in accordance with the above-mentioned measurement method are shown in Fig. 2 and Fig. 3 , respectively.
- the tan ⁇ of the layer A containing a thermoplastic elastomer can be measured by performing a dynamic viscoelasticity test at a frequency of 1,000 Hz in accordance with ASTM D4065-06.
- the temperature at which the peak maximum in tan ⁇ (frequency: 1,000 Hz) of the layer A appears is preferably -10°C or higher, more preferably -5°C or higher, and further more preferably 0°C or higher.
- the peak maximum in tan ⁇ (frequency: 1,000 Hz) of the layer A appears at a temperature lower than -10°C, the sound insulating properties tend to be difficult to exhibit in a temperature range in which it is used as a laminated glass, particularly, in a high temperature range.
- the temperature at which the peak maximum in tan ⁇ (frequency: 1,000 Hz) of the layer A appears is preferably 30°C or lower, more preferably 29°C or lower, and further more preferably 28°C or lower.
- the peak maximum in tan ⁇ (frequency: 1,000 Hz) of the layer A appears at a temperature higher than 30°C the sound insulating properties tend to be difficult to exhibit in a temperature range in which it is used as a laminated glass, particularly, in a low temperature range.
- the glass transition temperature of the thermoplastic elastomer to be used in the layer A is preferably 10°C or lower, and more preferably -5°C or lower.
- the lower limit of the glass transition temperature of the thermoplastic elastomer is not particularly limited, however, the glass transition temperature of the thermoplastic elastomer is preferably -50°C or higher, and more preferably -40°C or higher.
- DSC differential scanning calorimetry
- the height of at least one peak in tan ⁇ as measured by performing a dynamic viscoelasticity test at a frequency of 1,000 Hz in accordance with ASTM D4065-06 is preferably 1.3 or more, more preferably 1.5 or more, further more preferably 1.6 or more, and particularly preferably 1.7 or more.
- the height of the peak in tan ⁇ (frequency: 1,000 Hz) under the above conditions is less than 1.3, the sound insulating properties of a laminate to be obtained tend to be deteriorated, and particularly, the sound insulating properties in a thin laminated glass tend to be deteriorated.
- the shear storage modulus can be measured based on, for example, a dynamic viscoelasticity test at a frequency of 1,000 Hz in accordance with ASTM D4065-06 or a complex shear viscosity test in accordance with JIS K 7244-10.
- the shear storage modulus is an index of a component stored inside an object in energy generated from an external force and strain applied to the object and is obtained from a relationship between a dynamic modulus and a temperature at a constant temperature rising rate of the measurement temperature using a strain-controlled dynamic viscoelasticity apparatus.
- the measurement conditions for the shear storage modulus can be appropriately set, however, for example, the shear storage modulus can be measured by setting the frequency to 1 Hz and the temperature to -40°C or higher and 100°C or lower.
- JIS K 7244-10 there are a stress-controlled testing method and a strain-controlled testing method.
- a parallel-plate oscillatory rheometer can be used as a testing apparatus.
- the parallel-plate oscillatory rheometer is composed of two coaxial and rigid parallel disks. A test sheet is placed between the disks, and one disk is fixed and the other disk is oscillated at a constant frequency, whereby dynamic viscoelasticity characteristics such as a shear loss modulus and a shear storage modulus can be measured.
- the diameter of the disk is generally 20 mm or more and 50 mm or less, and the thickness of a test sheet is defined as a distance between the disks.
- a test sheet with a weight of about 3 g or more and 5 g or less is used, and the thickness of the test sheet is desirably in the range of 0.5 mm or more and 3 mm or less.
- the ratio of the diameter of the disk to the thickness of the test sheet is desirably in the range of 10 or more and 50 or less.
- the test sheet is formed into a disk shape by injection molding, compression molding, or cutting out from the sheet. Alternatively, a pellet, a liquid, or a molten polymer may be filled between the disks. Further, the gap between the two plates is completely filled with the test sheet.
- a sinusoidal displacement at a fixed angular frequency is applied, and the resulting sinusoidal torque and the phase difference between the torque and the angular displacement are measured.
- a torque measuring apparatus is connected to one plate and measures a torque necessary for deforming the test sheet.
- An angular displacement measuring apparatus is connected to the movable-side plate and measures an angular displacement and a frequency. To the test sheet, either a sinusoidal torque or an angular displacement is applied at a constant frequency, and from the measured torque and displacement, and the dimensions of the test sheet, the shear loss modulus and shear storage modulus are determined.
- test temperature is desirably measured by bringing a thermometer into contact with the fixed-side disk or burying a thermometer therein.
- the heating is performed by forced convection, high frequency heating, or an appropriate method.
- the test sheet and the disks are sufficiently maintained at the test temperature until they reach a thermal equilibrium state so that the measured values of the shear loss modulus and the shear storage modulus do not change.
- the equilibration time is desirably 15 minutes or more and 30 minutes or less.
- the shear storage modulus of the layer A at 70°C as measured by performing a dynamic viscoelasticity test at a frequency of 1,000 Hz in accordance with ASTM D4065-06 is 1 MPa or more, and preferably 1.1 MPa or more. If the shear storage modulus (at a frequency of 1,000 Hz and 70°C) of the layer A is less than 1 MPa, when the surface of the interlayer film for laminated glass is shaped, optical unevenness at an interface between the layers of the interlayer film for laminated glass is likely to occur.
- Examples of a method for setting the shear storage modulus (at a frequency of 1,000 Hz and 70°C) of the layer A to 1 MPa or more include a method in which the content of the hard segment block in the thermoplastic elastomer is set to 5 mass% or more.
- the content of the hard segment block in the thermoplastic elastomer is preferably 40 mass% or less.
- the shear storage modulus (at a frequency of 1,000 Hz and 70°C) of the layer A is preferably 5 MPa or less, and more preferably 3 MPa or less.
- the shear storage modulus (at a frequency of 1 Hz and 70°C) of the layer A is 5 MPa or less, the sound insulating properties at around room temperature tends to be excellent.
- the elastic limit of the layer A in the interlayer film for laminated glass of the invention at 20°C is preferably 4 N or more, more preferably 5 N or more, and further more preferably 6 N or more. If the elastic limit of the layer A at 20°C is less than 4 N, when the surface of the interlayer film for laminated glass is shaped, optical unevenness at an interface between the layers of the interlayer film for laminated glass tends to easily occur.
- Examples of a method for setting the elastic limit of the layer A at 20°C to 4 N or more include a method in which the content of the hard segment block in the thermoplastic elastomer is set to 5 mass% or more.
- the content of the hard segment block in the thermoplastic elastomer is preferably 40 mass% or less.
- the elastic limit of the layer A at 20°C is preferably 25 N or less, and more preferably 15 N or less. When the elastic limit of the layer A at 20°C exceeds 25 N, the sound insulating properties at around room temperature are sometimes poor.
- the elastic limit of the layer A at 20°C refers to a yield point which can be obtained by measurement under the conditions that a distance between chucks is 50 mm and a tensile rate is 100 mm/min using, for example, an autograph AG-IS manufactured by Shimazu Corporation.
- the interlayer film for laminated glass of the invention has a layer having a higher shear storage modulus (at a frequency of 1,000 Hz and 70°C) than the layer A on at least one surface of the layer A.
- the shear storage modulus (at a frequency of 1,000 Hz and 70°C) of the layer having a higher shear storage modulus (at a frequency of 1,000 Hz and 70°C) than the layer A is preferably 1.1 MPa or more, more preferably 1.5 MPa or more, and further more preferably 2 MPa or more. Further, the shear storage modulus (at a frequency of 1,000 Hz and 70°C) thereof is preferably 500 MPa or less, and more preferably 400 MPa or less.
- the shear storage modulus (at a frequency of 1,000 Hz and 70°C) of the layer having a higher shear storage modulus (at a frequency of 1,000 Hz and 70°C) than the layer A falls within the above range, when the surface of the interlayer film for laminated glass is shaped, optical unevenness tends to be less likely to occur at an interface between the layers of the interlayer film for laminated glass.
- a difference in the shear storage modulus (at a frequency of 1,000 Hz and 70°C) between the layer A and the layer having a higher shear storage modulus (at a frequency of 1,000 Hz and 70°C) than the layer A is preferably 0.2 MPa or more, more preferably 5 MPa or more, and further more preferably 1.0 MPa or more. Further, the difference is preferably 500 MPa or less, and more preferably 400 MPa or less. If the difference falls within the above range, when the surface of the interlayer film for laminated glass is shaped, optical unevenness tends to be less likely to occur at an interface between the layers of the interlayer film for laminated glass.
- the layer having a higher shear storage modulus (at a frequency of 1,000 Hz and 70°C) than the layer A is preferably a layer B containing a thermoplastic resin.
- the thermoplastic resin refers to a polymer compound which is softened to exhibit plasticity when heated and is solidified when cooled, and is distinguished from a thermoplastic elastomer.
- thermoplastic resin is not particularly limited, however, examples thereof include a polyvinyl acetal resin, an ionomer resin, an ethylene-vinyl acetate copolymer resin, a vinyl chloride resin, a urethane resin, and a polyamide resin.
- the thermoplastic resin to be used in an outer layer is particularly preferably a polyvinyl acetal resin or an ionomer resin.
- the layer B contains the thermoplastic resin such as a polyvinyl acetal resin in an amount of preferably 40 mass% or more, more preferably 50 mass% or more, further more preferably 60 mass% or more, particularly preferably 80 mass% or more, and still further more preferably 90 mass% or more, and the layer B may be composed only of the thermoplastic resin such as a polyvinyl acetal resin.
- the content of the polyvinyl acetal resin in the layer B is less than 40 mass%, a desired shear storage modulus tends to be difficult to obtain.
- the polyvinyl acetal resin is preferably a polyvinyl acetal resin having an average acetalization degree of 40 mol% or more.
- the average acetalization degree of the polyvinyl acetal resin is more preferably 60 mol% or more, and further more preferably 65 mol% or more from the viewpoint of water resistance.
- the polyvinyl acetal resin is preferably a polyvinyl acetal resin having an average acetalization degree of 90 mol% or less.
- the average acetalization degree of the polyvinyl acetal resin is more preferably 85 mol% or less, and further more preferably 80 mol% or less from the viewpoint of water resistance.
- the polyvinyl acetal resin is preferably a polyvinyl acetal resin in which the content of the vinyl acetate unit in the polyvinyl acetal resin is 30 mol% or less. When the content of the vinyl acetate unit exceeds 30 mol%, blocking is likely to occur in the production of the resin, and therefore, it becomes difficult to produce the resin.
- the content of the vinyl acetate unit in the polyvinyl acetal resin is preferably 20 mol% or less.
- the polyvinyl acetal resin is generally constituted by a vinyl acetal unit, a vinyl alcohol unit, and a vinyl acetate unit, and the amount of each of these units can be measured in accordance with, for example, JIS K 6728 "Testing method for polyvinyl butylal” or by nuclear magnetic resonance spectroscopy (NMR).
- the amount of a vinyl alcohol unit and the amount of a vinyl acetate unit are measured, and the total amount of these units is subtracted from the amount of the vinyl acetal unit in the case where a unit other than the vinyl acetal unit is not contained, whereby the amount of the residual vinyl acetal unit can be calculated.
- the polyvinyl acetal resin can be produced by a conventionally known method, and typically produced by acetalization of polyvinyl alcohol using an aldehyde. Specific examples include the following method. Polyvinyl alcohol is dissolved in warm water, and while maintaining the resulting aqueous solution at a predetermined temperature, for example, 0°C or higher and 90°C or lower, preferably 10°C or higher and 20°C or lower, a necessary acid catalyst and an aldehyde are added thereto, and an acetalization reaction is allowed to proceed while stirring the resulting mixture. Then, the reaction temperature is increased to 70°C to effect aging, and thus, the reaction is completed. Thereafter, neutralization, washing with water, and drying are performed, whereby a polyvinyl acetal resin powder is obtained.
- a predetermined temperature for example, 0°C or higher and 90°C or lower, preferably 10°C or higher and 20°C or lower
- a necessary acid catalyst and an aldehyde are added thereto
- the viscosity-average polymerization degree of the polyvinyl alcohol to be used as a starting material of the polyvinyl acetal resin is preferably 100 or more, more preferably 300 or more, further more preferably 400 or more, still further more preferably 600 or more, particularly preferably 700 or more, and most preferably 750 or more.
- the viscosity-average polymerization degree of the polyvinyl alcohol is too low, the penetration resistance and heat creep resistance, particularly the heat creep resistance under high-temperature and high-humidity conditions such as 85°C and 85% RH are sometimes deteriorated.
- the viscosity-average polymerization degree of the polyvinyl alcohol is preferably 5,000 or less, more preferably 3,000 or less, further more preferably 2,500 or less, particularly preferably 2,300 or less, and most preferably 2,000 or less.
- the viscosity-average polymerization degree of the polyvinyl alcohol exceeds 5,000, it becomes difficult to mold a resin layer.
- a material containing the polyvinyl acetal resin as the main component for forming the layer B can be obtained by laminating a material, in which a polyvinyl acetal resin, particularly a polyvinyl butyral resin is used, the viscosity-average polymerization degree and the acetalization degree are optimized, and a small amount of a plasticizer is used or no plasticizer is used, with the layer A.
- the viscosity-average polymerization degree of the polyvinyl acetal resin coincides with the viscosity-average polymerization degree of the polyvinyl alcohol to be used as the starting material, and therefore, the preferred viscosity-average polymerization degree of the above-mentioned polyvinyl alcohol coincides with the preferred viscosity-average polymerization degree of the polyvinyl acetal resin.
- the amount of the vinyl acetate unit in the obtained polyvinyl acetal resin is preferred to 30 mol% or less, and therefore, it is preferred to use polyvinyl alcohol having a saponification degree of 70 mol% or more.
- the saponification degree of the polyvinyl alcohol is less than 70 mol%, the transparency or heat resistance of the resin is sometimes deteriorated, and also the reactivity with an aldehyde is sometimes decreased.
- the saponification degree thereof is more preferably 95 mol% or more.
- the viscosity-average polymerization degree and the saponification degree of the polyvinyl alcohol can be measured in accordance with, for example, JIS K 6726 "Testing method for polyvinyl alcohol".
- the aldehyde to be used for acetalization of the polyvinyl alcohol is preferably an aldehyde having a carbon number of 1 or more and 12 or less.
- the number of carbon atoms in the aldehyde exceeds 12
- the acetalization reactivity is decreased, and moreover, during the reaction, a resin block is likely to be formed, and thus, the synthesis of the resin is likely to involve difficulties.
- the aldehyde is not particularly limited, and examples thereof include aliphatic, aromatic, and alicyclic aldehydes such as formaldehyde, acetaldehyde, propionaldehyde, n-butyraldehyde, isobutyraldehyde, valeraldehyde, n-hexylaldehyde, 2-ethylbutyraldehyde, n-heptylaldehyde, n-octylaldehyde, n-nonylaldehyde, n-decylaldehyde, benzaldehyde, and cinnamaldehyde.
- aldehyde is not particularly limited, and examples thereof include aliphatic, aromatic, and alicyclic aldehydes such as formaldehyde, acetaldehyde, propionaldehyde, n-butyraldehyde, isobutyral
- an aliphatic aldehyde having a carbon number of 2 or more and 6 or less is preferred, and above all, butyraldehyde is particularly preferred.
- the above aldehydes may be used alone or two or more types may be used in combination.
- small amounts of multifunctional aldehydes, aldehydes having other functional groups, and the like may be used in combination within the range of 20 mass% or less of the total aldehydes.
- the ionomer is not particularly limited as long as it is a resin, which has an ethylene-derived constituent unit and an ⁇ , ⁇ -unsaturated carboxylic acid-derived constituent unit, and in which the ⁇ , ⁇ -unsaturated carboxylic acid is at least partially neutralized with a metal ion.
- the metal ion include a sodium ion.
- the content ratio of the ⁇ , ⁇ -unsaturated carboxylic acid constituent unit is preferably 2 mass% or more, and more preferably 5 mass% or more.
- the content ratio of the ⁇ , ⁇ -unsaturated carboxylic acid constituent unit is preferably 30 mass% or less, and more preferably 20 mass% or less.
- an ionomer of an ethylene-acrylic acid copolymer and an ionomer of an ethylene-methacrylic acid copolymer are preferred.
- an ethylene-based ionomer a sodium ionomer of an ethylene-acrylic acid copolymer and a sodium ionomer of an ethylene-methacrylic acid copolymer can be exemplified as particularly preferred examples.
- Examples of the ⁇ , ⁇ -unsaturated carboxylic acid constituting the ionomer include acrylic acid, methacrylic acid, maleic acid, monomethyl maleate, monoethyl maleate, and maleic anhydride. However, acrylic acid and methacrylic acid are particularly preferred.
- thermoplastic resin such as a polyvinyl acetal resin
- a heat shielding material a UV absorber, a plasticizer, an antioxidant, a light stabilizer, an adhesive strength adjusting agent, a blocking inhibitor, a pigment, a dye, or the like may be added as needed.
- the heat shielding material (for example, inorganic heat shielding fine particles or an organic heat shielding material) may be contained in the layer B.
- the heat shielding fine particles the same heat shielding fine particles as the ones which can be contained in the layer A can be used.
- the infrared absorbing ability of the heat shielding material is proportional to the optical path length (m) when infrared light passes through the layer B and the concentration (g/m 3 ) of the heat shielding material in the layer B. Therefore, the infrared absorbing ability of the heat shielding material is proportional to the area density (g/m 2 ) of the heat shielding material in the layer B.
- the area density (g/m 2 ) of the heat shielding material is preferably 0.10 or more, more preferably 0. 15 or more, and further more preferably 0.20 or more.
- the area density (g/m 2 ) of the heat shielding material in the layer B is less than 0.10, a sufficient heat shielding effect tends to be difficult to obtain.
- the area density (g/m 2 ) of the heat shielding material is preferably 1.00 or less, more preferably 0.70 or less, and further more preferably 0.50 or less.
- the area density (g/m 2 ) of the heat shielding material in the layer B exceeds 1.00, in the case where a laminated glass is formed, the visible light transmittance tends to be decreased, the haze tends to be deteriorated, the weather resistance tends to be decreased, or the change in color difference tends to be increased.
- the area density (g/m 2 ) of the heat shielding material is preferably 0.50 or more, more preferably 1.00 or more, further more preferably 1.50 or more, particularly preferably 2.25 or more, and most preferably 3. 00 or more.
- the area density (g/m 2 ) of the heat shielding material is preferably 15.00 or less, more preferably 10.50 or less, and further more preferably 7.50 or less.
- the area density (g/m 2 ) of the heat shielding material is preferably 1.00 or more, more preferably 1. 50 or more, and further more preferably 2.00 or more.
- the area density (g/m 2 ) of the heat shielding material is preferably 10.00 or less, more preferably 7.00 or less, and further more preferably 5.00 or less.
- the area density (g/m 2 ) of the heat shielding material is preferably 0.010 or more, more preferably 0.015 or more, and further more preferably 0.020 or more.
- the area density (g/m 2 ) of the heat shielding material is preferably 0.100 or less, more preferably 0.070 or less, and further more preferably 0.050 or less.
- the area density (g/m 2 ) of the heat shielding material is preferably 1.00 or more, more preferably 1.50 or more, and further more preferably 2.00 or more.
- the area density (g/m 2 ) of the heat shielding material is preferably 10.00 or less, more preferably 7.00 or less, and further more preferably 5.00 or less.
- the area density (g/m 2 ) of the heat shielding material is preferably 1.00 or more, more preferably 1.50 or more, and further more preferably 2.00 or more.
- the area density (g/m 2 ) of the heat shielding material is preferably 10.00 or less, more preferably 7.00 or less, and further more preferably 5.00 or less.
- the area density (g/m 2 ) of the heat shielding material is preferably 0.02 or more, more preferably 0.03 or more, and further more preferably 0.04 or more.
- the area density (g/m 2 ) of the heat shielding material is preferably 0.20 or less, more preferably 0.14 or less, and further more preferably 0.10 or less.
- a heat shielding material is contained in the layer B.
- at least one type of UV absorber is further contained in at least the layer B.
- the interlayer film for laminated glass of the invention has a three-layer structure of layer B/layer A/layer B using the layer B as an outer layer
- a heat shielding material is contained in the layer B, infrared light passes through the optical path length of the two layers B, and therefore, the heat shielding properties can be enhanced without deteriorating the visible light transmittance or haze of the laminated glass.
- a UV absorber is contained in at least the layer B.
- the layer A when the layer A is used as an inner layer, the layer A can be protected from UV light.
- the deterioration of the haze or the decrease in the weather resistance can be prevented, or the change in color difference can be suppressed.
- UV absorber which can be used in the layer B include the same UV absorbers as the ones which may be contained in the layer A.
- the area density (g/m 2 ) of the UV absorber in the layer B is preferably 0.2 or more, more preferably 0.5 or more, and further more preferably 0.7 or more.
- the area density (g/m 2 ) of the UV absorber in the layer B is less than 0.1, in the case where a laminated glass is formed, the haze tends to be deteriorated, the weather resistance tends to be decreased, or the change in color difference tends to be increased.
- the area density (g/m 2 ) of the UV absorber in the layer B is preferably 10.0 or less, more preferably 5.0 or less, and further more preferably 3.0 or less.
- the area density (g/m 2 ) of the UV absorber in the layer B exceeds 10.0, in the case where a laminated glass is formed, the visible light transmittance tends to be decreased, the haze tends to be deteriorated, the weather resistance tends to be decreased, or the change in color difference tends to be increased.
- the addition amount of the UV absorber is preferably 10 ppm or more, and more preferably 100 ppm or more on a mass basis with respect to the thermoplastic resin contained in the layer B.
- the addition amount is less than 10 ppm, it is sometimes difficult to exhibit a sufficient effect.
- the UV absorber two or more types can be used in combination.
- the addition amount of the UV absorber is preferably 50, 000 ppm or less, and more preferably 10, 000 ppm or less on a mass basis with respect to the thermoplastic resin contained in the layer B. Even if the addition amount is set to more than 50,000 ppm, a marked effect cannot be expected.
- the plasticizer is not particularly limited, and a carboxylic acid ester-based plasticizer such as a monovalent carboxylic acid ester-based plasticizer or a polyvalent carboxylic acid ester-based plasticizer; a phosphoric acid ester-based plasticizer, an organic phosphite-based plasticizer, or the like, and other than these, a polymeric plasticizer such as a carboxylic acid polyester-based plasticizer, a carbonic acid polyester-based plasticizer, or a polyalkylene glycol-based plasticizer; or a hydroxycarboxylic acid ester-based plasticizer such as an ester compound of a hydroxycarboxylic acid and a polyhydric alcohol such as castor oil or an ester compound of a hydroxycarboxylic acid and a monohydric alcohol can also be used.
- a carboxylic acid ester-based plasticizer such as a monovalent carboxylic acid ester-based plasticizer or a polyvalent carboxylic acid ester-based plasticizer
- the monovalent carboxylic acid ester-based plasticizer is a compound obtained by a condensation reaction of a monovalent carboxylic acid such as butanoic acid, isobutanoic acid, hexanoic acid, 2-ethylbutanoic acid, heptanoic acid, octylic acid, 2-ethylhexanoic acid, or lauric acid with a polyhydric alcohol such as ethylene glycol, diethylene glycol, triethylene glycol, tetraethylene glycol, polyethylene glycol, polypropylene glycol, or glycerin, and specific examples of the compound include triethylene glycol di-2-diethylbutanoate, triethylene glycol diheptanoate, triethylene glycol di-2-ethylhexanoate, triethylene glycol dioctanoate, tetraethylene glycol di-2-ethylbutanoate, tetraethylene glycol diheptanoate, tetraethylene glycol
- polyvalent carboxylic acid ester-based plasticizer examples include compounds obtained by a condensation reaction of a polyvalent carboxylic acid such as adipic acid, succinic acid, azelaic acid, sebacic acid, phthalic acid, isophthalic acid, terephthalic acid, or trimellitic acid with an alcohol having 1 to 12 carbon atoms such as methanol, ethanol, butanol, hexanol, 2-ethylbutanol, heptanol, octanol, 2-ethylhexanol, decanol, dodecanol, butoxyethanol, butoxyethoxyethanol, or benzyl alcohol.
- a polyvalent carboxylic acid such as adipic acid, succinic acid, azelaic acid, sebacic acid, phthalic acid, isophthalic acid, terephthalic acid, or trimellitic acid
- an alcohol having 1 to 12 carbon atoms such as methanol, ethanol,
- the compound examples include dihexyl adipate, di-2-ethylbutyl adipate, diheptyl adipate, dioctyl adipate, di-2-ethylhexyl adipate, di(butoxyethyl) adipate, di(butoxyethoxyethyl) adipate, mono(2-ethylhexyl) adipate, dibutyl sebacate, dihexyl sebacate, di-2-ethylbutyl sebacate, dibutyl phthalate, dihexyl phthalate, di(2-ethylbutyl) phthalate, dioctyl phthalate, di(2-ethylhexyl) phthalate, benzylbutyl phthalate, and didodecyl phthalate.
- Examples of the phosphoric acid-based plasticizer or the phosphorous acid-based plasticizer include compounds obtained by a condensation reaction of phosphoric acid or phosphorous acid with an alcohol having 1 to 12 carbon atoms such as methanol, ethanol, butanol, hexanol, 2-ethylbutanol, heptanol, octanol, 2-ethylhexanol, decanol, dodecanol, butoxyethanol, butoxyethoxyethanol, or benzyl alcohol.
- an alcohol having 1 to 12 carbon atoms such as methanol, ethanol, butanol, hexanol, 2-ethylbutanol, heptanol, octanol, 2-ethylhexanol, decanol, dodecanol, butoxyethanol, butoxyethoxyethanol, or benzyl alcohol.
- the compound examples include trimethyl phosphate, triethyl phosphate, tripropyl phosphate, tributyl phosphate, tri(2-ethylhexyl) phosphate, tri(butoxyethyl) phosphate, and tri(2-ethylhexyl) phosphite.
- the carboxylic acid polyester-based plasticizer may be a carboxylic acid polyester obtained by alternating copolymerization of a polyvalent carboxylic acid such as oxalic acid, malonic acid, succinic acid, adipic acid, suberic acid, sebacic acid, dodecanedioic acid, 1,2-cyclohexanedicarboxylic acid, 1,3-cyclohexanedicarboxylic acid, or 1,4-cyclohexanedicarboxylic acid with a polyhydric alcohol such as ethylene glycol, diethylene glycol, triethylene glycol, tetraethylene glycol, 1,2-propylene glycol, 1,3-propylene glycol, 1,2-butylene glycol, 1,3-butylene glycol, 1,4-butylene glycol, 1,2-pentanediol, 1,5-pentanediol, 2,4-pentanediol, 1,2-hexanediol, 1,6-hexan
- the terminal structure of such a carboxylic acid polyester is not particularly limited and may be a hydroxy group or a carboxyl group, or the terminal hydroxy group or the terminal carboxyl group may be reacted with a monovalent carboxylic acid or a monohydric alcohol to form an ester bond.
- Examples of the carbonic acid polyester-based plasticizer include a carbonic acid polyester obtained by alternating copolymerization of a polyhydric alcohol such as ethylene glycol, diethylene glycol, triethylene glycol, tetraethylene glycol, 1,2-propylene glycol, 1,3-propylene glycol, 1,2-butylene glycol, 1,3-butylene glycol, 1,4-butylene glycol, 1,2-pentanediol, 1,5-pentanediol, 2,4-pentanediol, 1,2-hexanediol, 1,6-hexanediol, 3-methyl-1,5-pentanediol, 3-methyl-2,4-pentanediol, 1,2-heptanediol, 1,7-heptanediol, 1,2-octanediol, 1,8-octanediol, 1,2-nonanediol, 1,9-nonan
- polyalkylene glycol-based plasticizer examples include a polymer obtained by ring-opening polymerization of an alkylene oxide such as ethylene oxide, propylene oxide, butylene oxide, or oxetane using a monohydric alcohol, a polyhydric alcohol, a monovalent carboxylic acid, or a polyvalent carboxylic acid as an initiator.
- hydroxycarboxylic acid ester-based plasticizer a monohydric alcohol ester of a hydroxycarboxylic acid (such as methyl ricinoleate, ethyl ricinoleate, butyl ricinoleate, methyl 6-hydroxyhexanoate, ethyl 6-hydroxyhexanoate, or butyl 6-hydroxyhexanoate), or a polyhydric alcohol ester of a hydroxycarboxylic acid [such as ethylene glycol di(6-hydroxyhexanoic acid) ester, diethylene glycol di(6-hydroxyhexanoic acid) ester, triethylene glycol di(6-hydroxyhexanoic acid) ester, 3-methyl-1,5-pentanediol di(6-hydroxyhexanoic acid) ester, 3-methyl-1,5-pentanediol di(2-hydroxybutyric acid) ester, 3-methyl-1,5-pentanediol di(3-)
- these plasticizers may be used alone or a two or more types may be used in combination.
- a plasticizer is contained in the layer B, from the viewpoint of compatibility of the plasticizer with the resin (particularly the polyvinyl acetal resin) to be used in the layer B, a low transferability to another layer, and the enhancement of nontransferability, it is preferred to use an ester-based plasticizer or an ether-based plasticizer which has a melting point of 30°C or lower and a hydroxyl value of 15 mgKOH/g or more and 450 mgKOH/g or less, or an ester-based plasticizer or an ether-based plasticizer which is amorphous and has a hydroxyl value of 15 mgKOH/g or more and 450 mgKOH/g or less.
- the term "amorphous" refers to that the melting point is not observed at a temperature of -20°C or higher.
- the hydroxyl value is preferably 15 mgKOH/g or more, more preferably 30 mgKOH/g or more, and most suitably 45 mgKOH/g or more. Further, the hydroxyl value is preferably 450 mgKOH/g or less, more preferably 360 mgKOH/g or less, and most suitably 280 mgKOH/g or less.
- ester-based plasticizer examples include polyesters (the above-mentioned carboxylic acid polyester-based plasticizer, carbonic acid polyester-based plasticizer, and the like) and hydroxycarboxylic acid ester compounds (the above-mentioned hydroxycarboxylic acid ester-based plasticizer and the like) satisfying the above conditions
- ether-based plasticizer examples include polyether compounds (the above-mentioned polyalkylene glycol-based plasticizer and the like) satisfying the above conditions.
- the content of the plasticizer is preferably 50 parts by mass or less, more preferably 25 parts by mass or less, further more preferably 20 parts by mass or less, particularly preferably 10 parts by mass or less, more particularly preferably 6 parts by mass or less, and most preferably 0 parts by mass (that is, the plasticizer is not contained) with respect to 100 parts by mass of the thermoplastic resin such as a polyvinyl acetal resin or an ethylene-vinyl acetate copolymer or an ionomer resin.
- the content of the plasticizer exceeds 50 parts by mass, the shear storage modulus of the layer B and the laminate tends to be decreased.
- two or more types of plasticizers may be used in combination.
- the plasticizer a compound having a hydroxy group can be used, however, the ratio of the content of the compound having a hydroxy group with respect to the total amount of the plasticizer to be used in the layer B is preferably 10 mass% or more, more preferably 15 mass% or more, and further more preferably 20 mass% or more.
- the ratio of the content of the compound having a hydroxy group with respect to the total amount of the plasticizer to be used in the layer B is preferably 100 mass% or less, more preferably 99 mass% or less, and further more preferably 98 mass% or less.
- the compound having a hydroxy group has high compatibility with a polyvinyl acetal resin and has low transferability to another resin layer, and therefore, the compound having a hydroxy group can be favorably used.
- the same antioxidant as the one which is contained in the layer A is used.
- the antioxidants can be used alone or two or more types can be used in combination.
- the area density of the antioxidant in the layer B is preferably 0.1 g/m 2 or more, more preferably 0.2 g/m 2 or more, and further more preferably 0.5 g/m 2 or more.
- the area density of the antioxidant in the layer B is less than 0.1 g/m 2 , the layer B is easily oxidized, and in the case where the laminated glass is used for a long period of time, the change in color difference is increased, and so on, and thus, the weather resistance tends to be decreased.
- the area density of the antioxidant in the layer B is preferably 2.5 g/m 2 or less, more preferably 1.5 g/m 2 or less, and further more preferably 2.0 g/m 2 or less.
- the area density of the antioxidant in the layer B exceeds 2.5 g/m 2 , the color tone of the layer B tends to be impaired or the haze of the laminated glass tends to be decreased.
- the blending amount of the antioxidant is preferably 0.001 parts by mass or more, and more preferably 0.01 parts by mass or more with respect to 100 parts by mass of the polyvinyl acetal resin.
- amount of the antioxidant is less than 0.001 parts by mass, it is sometimes difficult to exhibit a sufficient effect.
- the blending amount of the antioxidant is preferably 5 parts by mass or less, more preferably 4 parts by mass or less, and most preferably 3 parts by mass or less with respect to 100 parts by mass of the polyvinyl acetal resin. Even if the amount of the antioxidant is set to more than 5 parts by mass, a marked effect cannot be expected.
- the same light stabilizer as the one which is contained in the layer A is used.
- the blending amount of the light stabilizer is preferably 0.01 parts by mass or more, and more preferably 0.05 parts by mass or more with respect to 100 parts by mass of the thermoplastic resin such as a polyvinyl acetal resin.
- the content of the light stabilizer is preferably 10 parts by mass or less, and more preferably 5 parts by mass or less. Even if the amount of the light stabilizer is set to more than 10 parts by mass, a marked effect cannot be expected.
- the area density of the light stabilizer in the layer B is preferably 0.05 g/m 2 or more, and more preferably 0.5 g/m 2 or more. Further, the area density is preferably 70 g/m 2 or less, and more preferably 30 g/m 2 or less.
- an adhesive strength adjusting agent and/or any of various additives for adjusting the adhesiveness may be contained in the layer B as needed.
- an alkali metal salt or an alkaline earth metal salt is preferably used, and examples thereof include salts of potassium, sodium, magnesium, and the like.
- the salts include salts of organic acids such as carboxylic acids such as octanoic acid, hexanoic acid, butyric acid, acetic acid, and formic acid; and inorganic acids such as hydrochloric acid and nitric acid.
- each of the adhesive strength adjusting agent and/or the various additives for adjusting the adhesiveness varies depending on the additive to be used, however, it is preferred to adjust the adhesive strength of the interlayer film for laminated glass to be obtained to a glass as measured by the Pummel test (described in WO 03/033583 ) to generally 3 or more and 10 or less, and to 3 or more and 6 or less in the case where particularly high penetration resistance is needed, and to 7 or more and 10 or less in the case where high shatterproof properties are needed.
- a method in which the adhesive strength adjusting agent is not added is also a useful method.
- At least one surface of the interlayer film for laminated glass is shaped.
- an air bubble present at an interface between the interlayer film for laminated glass and a glass easily escapes to the outside of the laminated glass, and thus, the appearance of the laminated glass can be made favorable.
- Examples of a method for shaping the surface of the interlayer film for laminated glass include a conventionally known embossing roll method, a profile extrusion method, and an extrusion lip embossing method utilizing melt fracture.
- an embossing roll method is preferred for stably obtaining the interlayer film for laminated glass having uniform and fine concave and convex portions formed thereon.
- An embossing roll to be used in the embossing roll method can be produced by, for example, using an engraving mill (mother mill) having a desired concave-convex pattern and transferring the concave-convex pattern to the surface of a metal roll. Further, an embossing roll can also be produced using laser etching. Further, after forming a fine concave-convex pattern on the surface of a metal roll as described above, the surface with the fine concave-convex pattern is subjected to a blast treatment using an abrasive material such as aluminum oxide, silicon oxide, or glass beads, whereby a finer concave-convex pattern can also be formed.
- the embossing roll to be used in the embossing roll method is preferably subjected to a release treatment.
- a release treatment In the case where an embossing roll which is not subjected to a release treatment is used, it becomes difficult to release the interlayer film for laminated glass from the embossing roll.
- Examples of a method for the release treatment include known methods such as a silicone treatment, a Teflon (registered trademark) treatment, and a plasma treatment.
- the depth of the concave portion and/or the height of the convex portion (hereinafter sometimes referred to as "the height of the embossed portion") of the surface of the interlayer film for laminated glass shaped by an embossing roll method or the like are/is preferably 5 ⁇ m or more, more preferably 10 ⁇ m or more, and further more preferably 20 ⁇ m or more.
- the height of the embossed portion is 5 ⁇ m or more, in the case where a laminated glass is produced, an air bubble present at an interface between the interlayer film for laminated glass and a glass is less likely to remain, and thus, the appearance of the laminated glass tends to be improved.
- the height of the embossed portion is preferably 150 ⁇ m or less, more preferably 100 ⁇ m or less, and further more preferably 80 ⁇ m or less.
- the height of the embossed portion is 150 ⁇ m or less, in the case where a laminated glass is produced, the adhesiveness between the interlayer film for laminated glass and a glass becomes favorable, and thus, the appearance of the laminated glass tends to be improved.
- the height of the embossed portion refers to a maximum height roughness (Rz) defined in JIS B 0601 (2001).
- the height of the embossed portion can be measured by, for example, utilizing the confocal principle of a laser microscope or the like.
- the height of the embossed portion that is, the depth of the concave portion or the height of the convex portion may vary within a range that does not depart from the gist of the invention.
- Examples of the form of the shape imparted by an embossing roll method or the like include a lattice, an oblique lattice, an oblique ellipse, an ellipse, an oblique groove, and a groove.
- the form is preferably an oblique lattice, an oblique groove, or the like from the viewpoint that an air bubble more favorably escapes.
- the inclination angle is preferably from 10° to 80° with respect to the film flow direction (MD direction).
- the shaping by an embossing roll method or the like may be performed on one surface of the interlayer film for laminated glass, or may be performed on both surfaces, but is more preferably performed on both surfaces. Further, the shaping pattern may be a regular pattern or an irregular pattern.
- a laminate constituting the interlayer film for laminated glass of the invention can be favorably used also as the interlayer film for laminated glass having excellent sound insulating properties and heat shielding properties.
- the interlayer film for laminated glass is composed of a laminate in which the layer A described above is laminated between at least two layers B described above.
- the interlayer film for laminated glass of the invention is preferably such that in the case where a laminated glass in which the interlayer film is sandwiched between two clear glasses with the total thickness of the glasses being 4 mm or less is formed, the visible light transmittance thereof is 70% or more and the average transmittance of infrared light in the wavelength range of 800 to 1,100 nm thereof is 70% or less.
- an interlayer film for laminated glass satisfying the above configuration, it is preferred to form an interlayer film for laminated glass in which at least one layer A containing a thermoplastic elastomer is included and the above-mentioned heat shielding material is contained in at least one layer.
- the visible light transmittance thereof is preferably 70% or more, and more preferably 72% or more.
- the visible light transmittance in the case where a laminated glass is formed is less than 70%, the visibility of the laminated glass tends to be impaired.
- the average transmittance of infrared light in the wavelength range of 800 to 1, 100 nm thereof is preferably 70% or less, more preferably 59% or less, and further more preferably 58% or less.
- the heat shielding properties tend to be decreased.
- the interlayer film for laminated glass of the invention is preferably such that in the case where a laminated glass in which the interlayer film is sandwiched between two green glasses with the total thickness of the glasses being 4 mm or less is formed, the visible light transmittance thereof is 70% or more and the average transmittance of infrared light in the wavelength range of 800 to 1,100 nm thereof is 32% or less.
- an interlayer film for laminated glass satisfying the above configuration, it is preferred to form an interlayer film for laminated glass in which at least one layer A containing a thermoplastic elastomer is included and the above-mentioned heat shielding material is contained in at least one layer.
- the visible light transmittance thereof is preferably 70% or more, and more preferably 72% or more.
- the visible light transmittance in the case where a laminated glass is formed is less than 70%, the color tone of the laminated glass tends to be impaired.
- the average transmittance of infrared light in the wavelength range of 800 to 1, 100 nm thereof is preferably 32% or less, and more preferably 31% or less.
- the heat shielding properties tend to be decreased.
- the interlayer film for laminated glass of the invention is preferably such that in the case where a laminated glass in which the interlayer film is sandwiched between two glasses with the total thickness of the glasses being 4 mm or less is formed and a weathering test is performed for the laminated glass by exposure for 200 hours under the conditions that the irradiance is 180 W/m 2 , the black panel temperature is 60°C, and the relative humidity is 50%, the change in color difference ⁇ E*ab in accordance with JIS Z 8781-4: 2013 for the laminated glass between before and after the weathering test is 2.0 or less.
- an interlayer film for laminated glass satisfying the above configuration, it is preferred to form an interlayer film for laminated glass in which at least one layer A containing a thermoplastic elastomer is included and a heat shielding material is contained in at least one layer.
- the change in color difference ⁇ E*ab thereof is more preferably 1.8 or less, and further more preferably 1.5 or less.
- the change in color difference ⁇ E*ab thereof under the above conditions exceeds 2.0, the laminated glass tends to be easily discolored yellow by the long-term use thereof.
- the interlayer film for laminated glass of the invention is preferably such that in the case where a laminated glass in which the interlayer film is sandwiched between two glasses with the total thickness of the glasses being 4 mm or less is formed, the haze thereof is 5 or less.
- the haze thereof is more preferably 4 or less, further more preferably 3 or less, and particularly preferably 2 or less.
- the haze thereof exceeds 5, the transparency is decreased, so that it tends not to be suitable for a laminated glass for a car or the like.
- the interlayer film for laminated glass of the invention is preferably such that in the case where a laminated glass in which the interlayer film is sandwiched between two glasses is formed, the sound transmission loss thereof at 4,000 Hz as measured under the conditions of ASTM E 90-09 (Standard Test Method for Laboratory Measurement of Airborne Sound Transmission Loss of Building Partitions and Elements) is 37 dB or more.
- ASTM E 90-09 Standard Test Method for Laboratory Measurement of Airborne Sound Transmission Loss of Building Partitions and Elements
- the sound transmission loss thereof at 4,000 Hz as measured under the conditions of ASTM E 90-09 is more preferably 38 dB or more, and further more preferably 40 dB or more. Also in the case where a laminated glass in which the interlayer film is sandwiched between two glasses with the total thickness of the glasses being 4 mm or less is formed, it is preferred to satisfy the above sound transmission loss.
- the ratio of the total thickness of the layer A to the total thickness of the layer B constituting the interlayer film for laminated glass of the invention is preferably 1/30 or more, more preferably 1/15 or more, further more preferably 1/8 or more, and still further more preferably 1/5 or more.
- the ratio is 1/30 or more, the sound insulating effect of the interlayer film for laminated glass tends to be improved.
- the ratio of the total thickness of the layer A to the total thickness of the layer B is preferably 1/1 or less, more preferably 1/2 or less, and further more preferably 1/3 or less.
- the ratio is 1/1 or less, the heat creep resistance of the interlayer film for laminated glass and the bending strength when a laminated glass is formed tend to be improved.
- the laminate constituting the interlayer film for laminated glass of the invention may have a two-layer structure of layer A/layer B, or can have a laminated structure in which the layer A (1) is sandwiched between the layer B (2a) and the layer B (2b) as shown in Fig. 1 .
- the laminated structure of the laminate can be determined according to the intended use, however, other than a laminated structure of layer B/layer A/layer B, a laminated structure of layer B/layer A/layer B/layer A or layer B/layer A/layer B/layer A/layer B may be adopted.
- At least one layer (named "layer C") other than the layer A and the layer B may be included, and for example, a laminated structure of layer B/layer A/layer C/layer B, layer B/layer A/layer B/layer C, layer B/layer C/layer A/layer C/layer B, layer B/layer C/layer A/layer B/layer C, layer B/layer A/layer C/layer B/layer C, layer C/layer B/layer A/layer B/layer C, layer C/layer B/layer A/layer C/layer B/layer C, layer C/layer B/layer C/layer A/layer C/layer B/layer C, or the like may be adopted.
- the components in the layer C may be the same or different. The same shall apply also to the components in the layer A or the layer B.
- a layer composed of a known resin can be used, and for example, polyethylene, polypropylene, polyvinyl chloride, polystyrene, polyvinyl acetate, polyurethane, polytetrafluorethylene, an acrylic resin, polyamide, polyacetal, polycarbonate, polyester (polyethylene terephthalate or polybutylene terephthalate), a cyclic polyolefin, polyphenylene sulfide, polytetrafluoroethylene, polysulfone, polyethersulfone, polyarylate, a liquid crystalline polymer, polyimide, or the like can be used.
- a known resin for example, polyethylene, polypropylene, polyvinyl chloride, polystyrene, polyvinyl acetate, polyurethane, polytetrafluorethylene, an acrylic resin, polyamide, polyacetal, polycarbonate, polyester (polyethylene terephthalate or polybutylene terephthalate), a cycl
- an additive such as a plasticizer, an antioxidant, a UV absorber, a light stabilizer, an adhesive strength adjusting agent, a blocking inhibitor, a pigment, a dye, or a heat shielding material (for example, inorganic heat shielding fine particles or an organic heat shielding material having an infrared absorbing ability) may be added as needed.
- the heat shielding material may be contained in the layer B.
- the same heat shielding material as the one which can be contained in the layer A can be used.
- the content of the heat shielding material is preferably 0.1 mass% or more, and more preferably 0.2 mass% or more, and also preferably 5 mass% or less, and more preferably 3 mass% or less with respect to the total resin used in the layer constituting the laminate.
- the average particle diameter of the inorganic heat shielding fine particles is preferably 100 nm or less, and more preferably 50 nm or less from the viewpoint of transparency.
- the average particle diameter of the inorganic heat shielding fine particles as used herein refers to a value measured with a laser diffractometer.
- a production method for the laminate constituting the interlayer film for laminated glass of the invention is not particularly limited, and another additive is blended in the above-mentioned thermoplastic resin or thermoplastic elastomer as needed, and the resulting mixture is uniformly kneaded, the respective layers such as the layer A and the layer B are formed by a known film forming method such as an extrusion method, a calendaring method, a pressing method, a casting method, or an inflation method, and these layers may be laminated, or the layer A, the layer B, and another necessary layer may be molded by a coextrusion method.
- a cooling roll it is preferred to set the temperature of a cooling roll to 20 to 100°C.
- the resin temperature during extrusion is preferably 150°C or higher, and more preferably 170°C or higher. Further, the resin temperature during extrusion is preferably 250°C or lower, and more preferably 230°C or lower.
- the resin temperature is too high, there is a concern that the polyvinyl acetal resin and the thermoplastic elastomer are decomposed to deteriorate the resin.
- the temperature is too low, the ejection from the extruder is not stable to cause a mechanical problem. In order to efficiently remove a volatile substance, it is preferred to remove the volatile substance by reducing pressure from the vent port of the extruder.
- the thickness of the laminate is preferably 20 ⁇ m or more, and more preferably 100 ⁇ m or more. When the thickness of the laminate is too thin, lamination cannot be favorably performed when a laminated glass is formed in some cases. Further, the thickness of the laminate is preferably 10, 000 ⁇ m or less, and more preferably 3,000 ⁇ m or less. When the thickness of the laminate is too thick, the cost is increased, and therefore, such a thickness is not preferred.
- the sound insulting properties of a laminated glass can be evaluated based on a loss factor obtained by a damping test using a central exciting method.
- the damping test is a test for evaluating how the loss factor changes depending on the frequency or temperature.
- the loss factor which reaches the maximum in a certain temperature range when the frequency is set constant is referred to as "maximum loss factor”.
- the maximum loss factor is an index indicating the goodness of the damping properties, and specifically is an index representing how fast the bending vibration generated on a plate-shaped object is damped. That is, it can be said that the maximum loss factor is used as an index of the sound insulating properties, and as the maximum loss factor of a laminated glass is higher, the sound insulating properties of the laminated glass is higher.
- a laminated glass is formed using the laminate as the interlayer film for laminated glass, and in the case where a damping test is performed for the obtained laminated glass by a central exciting method, the maximum loss factor at a frequency of 2,000 Hz and a temperature of 0°C or higher and 50°C or lower is preferably 0.20 or more, more preferably 0.25 or more, and further more preferably 0.28 or more.
- the maximum loss factor under the above conditions is less than 0.20, the sound insulating properties of the laminated glass is poor, so that it tends not to be suitable for use for the purpose of sound insulation.
- the laminated glass having a maximum loss factor as measured under the above conditions of 0.20 or more can be obtained by, for example, laminating a layer A including a composition containing an elastomer which has a peak maximum in tan ⁇ in the range of -40 to 30°C and a plurality of layers B having a shear storage modulus at a temperature of 25°C as measured by performing a complex shear viscosity test of 10.0 MPa or more such that the layer A is laminated between at least two layers B.
- the laminated glass of the invention is preferably a laminated glass which includes an interlayer film for laminated glass, in which at least one layer A containing a thermoplastic elastomer is included and a heat shielding material is contained in at least one layer, sandwiched between at least two glasses, and has a visible light transmittance of 70% or more and an average transmittance of infrared light in the wavelength range of 800 to 1,100 nm of 70% or less.
- a laminated glass satisfying the above configuration, it is preferred to form a laminated glass using an interlayer film for laminated glass in which at least one layer A containing a thermoplastic elastomer is included and a heat shielding material is contained in at least one layer.
- the heat shielding material is preferably at least one material selected from the group consisting of tin-doped indium oxide, antimony-doped tin oxide, zinc antimonate, metal-doped tungsten oxide, a phthalocyanine compound, aluminum-doped zinc oxide, and lanthanum hexaboride.
- the laminated glass of the invention can be favorably used for a glass for a windshield of a car, side windows of a car, a sunroof of a car, a head-up display, and the like. Further, the laminated glass of the invention can also be favorably used as a glass for construction.
- the shape of the cross section of the interlayer film for laminated glass to be used is preferably thick on one end face side and thin on the other end face side.
- the shape of the cross section may be a wedge as a whole such that the thickness gradually decreases from one end face side to the other end face side, or a part of the cross section may have the shape of a wedge such that the thickness is the same from one end face to an arbitrary position between the one end face and the other end face, and the thickness gradually decreases from the arbitrary position to the other end face.
- the thickness of the glass constituting the laminated glass of the invention is not particularly limited, but is preferably 100 mm or less. Further, since the interlayer film for laminated glass of the invention has excellent bending strength, even when the laminated glass is formed using a thin plate glass having a thickness of 2.8 mm or less, the strength of the laminated glass is not impaired, and thus, the reduction in the weight of the laminated glass can be realized. From the viewpoint of reduction in the weight, the thickness of at least one glass is preferably 2.8 mm or less, more preferably 2.5 mm or less, further more preferably 2.0 mm or less, and particularly preferably 1.8 mm or less.
- the thicknesses of the two glasses may be the same or different. For example, even when the thickness of one glass is set to 1.8 mm or more and the thickness of the other glass is set to 1.8 mm or less, and a difference in the thickness between the two glasses is set to 0.2 mm or more, a laminated glass in which optical unevenness is reduced can be formed without deteriorating the sound insulating properties, heat shielding properties, weather resistance, or the like of the laminated glass.
- the laminated glass of the invention can be produced by a conventionally known method.
- the method include a method using a vacuum laminator device, a method using a vacuum bag, a method using a vacuum ring, and a method using a nip roll. Further, a method of applying an autoclave step after temporary pressure bonding can also be additionally performed.
- a vacuum laminator device for example, a known apparatus to be used in the production of a solar battery is used, and lamination is performed under a reduced pressure of 1 ⁇ 10 -6 MPa or more and 3 ⁇ 10 -2 MPa or less at a temperature of 100°C or higher and 200°C or lower, particularly at a temperature of 130°C or higher and 170°C or lower.
- the method using a vacuum bag or a vacuum ring is described in, for example, European Patent No. 1235683 , and for example, lamination is performed under a pressure of about 2 ⁇ 10 -2 MPa at a temperature of 130°C or higher and 145°C or lower.
- Examples of the production method for the laminated glass include, in the case where a nip roll is used, a method in which first temporary pressure bonding is performed at a temperature equal to or lower than the flow initiation temperature of the polyvinyl acetal resin, and thereafter temporary pressure bonding is further performed under the conditions of a temperature close to the flow initiation temperature.
- Specific examples thereof include a method in which heating is performed at 30°C or higher and 100°C or lower by an infrared heater or the like, and thereafter, air is removed with a roll, and further heating is performed at 50°C or higher and 150°C or lower, and then, bonding or temporary bonding is performed by pressure bonding with a roll.
- the laminated glass may be formed by putting glasses in which the layer B is applied to both surfaces of the layer A together and laminating the glasses so that the interlayer film for laminated glass of the invention is included inside the laminated glass.
- the autoclave step to be performed additionally after temporary pressure bonding is performed, for example, under a pressure of about 1 MPa or more and 15 MPa or less at a temperature of 130°C or higher and 155°C or lower for about 0.5 hours or more and 2 hours or less, although depending on the thickness or structure of a module.
- the glass to be used when forming the laminated glass with the interlayer film for laminated glass of the invention is not particularly limited, and an inorganic glass such as a float plate glass, a polished plate glass, a figured plate glass, a wire-reinforced plate glass, or a heat-absorbing plate glass, and other than these, a conventionally known organic glass such as poly(methyl methacrylate) or polycarbonate, or the like can be used, and these may be either colorless or colored, or either transparent or non-transparent. These may be used alone or two or more types may be used in combination. Further, the thickness of the glass is not particularly limited, but is preferably 100 mm or less.
- polyvinyl butyral resin used in the following Examples and Comparative Examples, a resin obtained by acetalization of polyvinyl alcohol having a viscosity-average polymerization degree (a viscosity-average polymerization degree measured in accordance with JIS K 6726 "Testing method for polyvinyl alcohol") which is the same as the desired viscosity-average polymerization degree with n-butyl aldehyde in the presence of a hydrochloric acid catalyst was used.
- TPE-1 polystyrene-poly(isoprene/butadiene)-polystyrene triblock copolymer
- CWO cesium tungsten oxide
- the blending amounts were adjusted so that the area density of the heat shielding material in the layer A was 0.25 g/m 2 , the area density of the UV absorber in the layer A was 1.0 g/m 2 , the area density of the antioxidant in the layer A was 0.20 g/m 2 , and the area density of the light stabilizer in the layer A was 1.6 g/m 2 .
- Tinuvin 326 used as the UV absorber is 2-(5-chloro-2-benzotriazolyl)-6-tert-butyl-p-cresol (manufactured by Ciba Specialty Chemicals, Inc.).
- Cyanox 2777 used as the antioxidant is a mixture of 1,3,5-tris(4-tert-butyl-3-hydroxy-2,6-dimethylbenzyl)-1,3, 5-triazine-2,4,6-(1H,3H,5H)-trione and tris(2,4-di-t-butylphenyl)phosphate (manufactured by Cytec Industries Incorporated).
- Tinuvin 622SF used as the light stabilizer is a polymer of dimethyl succinate and 4-hydroxy-2,2,6,6-tetramethyl-1-piperidine ethanol (manufactured by Ciba Specialty Chemicals, Inc.).
- the main component refers to a component whose mass is the largest in the composition, and in the case where a plasticizer is contained, the component also including the plasticizer is referred to as "main component".
- polyvinyl butyral (PVB-1) having a viscosity-average polymerization degree of about 1,100, an acetalization degree of 68.7 mol%, a vinyl acetate unit content of 0.8 mol%, and a vinyl alcohol unit content of 30.5 mol% was used.
- Tinuvin 326 as a UV absorber was mixed, whereby a composition constituting the layer B was prepared.
- the composition was prepared by adjusting the blending amount so that the area density of the UV absorber in the layer B was 5.1 g/m 2 .
- the composition for the layer A was introduced into a T die (a multi-manifold type with a width of 500 mm) at 205°C under the conditions of a temperature of 210°C and an ejection amount of 4 kg/h using a vent-type single-screw extruder with a diameter of 50 mm, and the composition for the layer B was introduced into the T die under the conditions of a temperature of 205°C and an ejection amount of 24 kg/h using a vent-type single-screw extruder with a diameter of 65 mm.
- the molded material coextruded from the T die was nipped by two metallic mirror finish rolls, one of which was heated to 50°C and the other of which was heated to 60°C, and taken up at a take-up speed of 1.2 m/min, whereby an interlayer film (thickness: 760 ⁇ m) having a three-layer structure of layer B/layer A/layer B (thickness: 330 ⁇ m/100 ⁇ m/330 ⁇ m) was molded.
- the molded interlayer film (obtained laminate) was allowed to pass between a metal embossing roll (the inclination angle with respect to the laminate flow direction: 45°, the pitch: 150 ⁇ m, the width of a vertex portion of a convex portion: 50 ⁇ m, the width of a bottom portion of a concave portion: 30 ⁇ m, the height from a bottom portion of a concave portion to a vertex portion of a convex portion: 100 ⁇ m) and an elastic rubber roll, whereby an embossed pattern was formed on one surface thereof, and by allowing the laminate to pass therebetween again, an embossed pattern is formed on the other surface thereof.
- a metal embossing roll the inclination angle with respect to the laminate flow direction: 45°, the pitch: 150 ⁇ m, the width of a vertex portion of a convex portion: 50 ⁇ m, the width of a bottom portion of a concave portion: 30 ⁇ m, the height from a bottom portion of
- the molding was performed under the conditions that the temperature of the surface of the embossing roll was set to 80°C, the temperature of the surface of the elastic rubber roll was set to 30°C, the linear pressure between the embossing roll and the elastic rubber roll was set to 0.1 MPa, and the line speed was set to 0.5 m/min.
- the interlayer film for laminated glass obtained in Example 1 was sandwiched between two commercially available green glasses (50 mm (length) ⁇ 50 mm (width) ⁇ 1.6 mm (thickness)), and by using a vacuum laminator (1522N, manufactured by Nisshinbo Mechatronics, Inc.), a laminated glass was formed under the conditions that a hot plate temperature was 165°C, a vacuuming time was 12 minutes, a pressing pressure was 50 kPa, and a pressing time was 17 minutes.
- the obtained laminated glass was used for measuring the below-mentioned visible light transmittance, average infrared light transmittance, change in color difference, and haze.
- a mechanical spectrometer (model: DMA/SDTA861e, manufactured by Mettler Toledo, Inc.) was used.
- the composition for the layer A, the composition for the Layer B, and the main components of the layer A and the layer B (here, the polymer in each layer is the main component, however, as for the layers containing a plasticizer in the below-mentioned Examples and Comparative Examples, the polymer and the plasticizer are the main component) were separately hot-pressed at 210°C and 5 MPa for 5 minutes, whereby samples for evaluation were formed, and each sample was cut into a cylindrical shape having a thickness of 1 mm and a diameter of 3 to 10 mm (the diameter does not affect the result) and used as a test sample.
- the composition for the layer A obtained in Example 1 was pressed at 210°C and 5 MPa for 5 minutes, whereby the layer A having a thickness of 0.76 mm was molded.
- a test sample obtained by cutting the molded layer A into a width of 10 mm and a length of 100 mm was used for measuring the elastic limit of the layer A with an autograph AG-IS manufactured by Shimazu Corporation under the conditions that a distance between chucks was 50 mm and a tensile rate was 100 mm/min.
- the measurement result is shown in Table 3.
- the interlayer film for laminated glass 73 obtained in Example 1 was sandwiched between float glasses 71 and 72 having a length of 300 mm, a width of 100 mm, and a thickness of 3 mm, and by using a vacuum laminator (1522N, manufactured by Nisshinbo Mechatronics, Inc.), a laminated glass 70 was formed under the conditions that a hot plate temperature was 165°C, a vacuuming time was 12 minutes, a pressing pressure was 50 kPa, and a pressing time was 17 minutes.
- a vacuum laminator 1522N, manufactured by Nisshinbo Mechatronics, Inc.
- an iron plate 81 with a weight of 1 kg was bonded to one surface of the glass 72 using an instant adhesive, whereby a laminated glass 80 having an iron plato bonded thereto was formed.
- the laminated glass 80 was leaned against a stand 91 and left for 1 week in a chamber at 100°C. Thereafter, a distance that the glass 72 slid down was measured, and the distance was evaluated according to the following criteria, and the evaluation was regarded as the evaluation for the heat creep resistance.
- Example 2 50 mg of the hydrogenated product of the block copolymer obtained in Example 1 was dissolved in deuterated chloroform, and 1 H-NMR measurement was performed. The contents of 1,2-bonds and 3,4-bonds in an isoprene unit and a butadiene unit are measured, respectively, and the sum of the contents thereof was calculated. The calculation result of the sum of the contents of 1,2-bonds and 3,4-bonds in an isoprene unit and a butadiene unit is shown in Table 2.
- a mechanical spectrometer (model: DMA/SDTA861e, manufactured by Mettler Toledo, Inc.) was used for measuring the dynamic viscoelasticity of the interlayer film for laminated glass in accordance with ASTM D4065-06.
- the layer A and the layer B obtained in Example 1 were cut into a cylindrical shape having a thickness of 1 mm and a diameter of 3 to 5 mm (the diameter does not affect the result), respectively, and used as test samples.
- the presence or absence of optical unevenness was confirmed by observing the laminated glass by direct visual inspection. Further, S-light (manufactured by Nippon Gijutsu Center Co., Ltd.) was used as a light source, the laminated glass obtained above was disposed horizontally at a distance of 30 cm from the light source, light passing through the laminated glass was projected onto a white screen disposed at a distance of 70 cm from the laminated glass, and the presence or absence of optical unevenness was confirmed.
- the optical unevenness of the laminated glass was evaluated according to the following criteria. The evaluation result of the optical unevenness of the laminated glass is shown in Table 3.
- the surface of the interlayer film for laminated glass was measured using a Keyence laser microscope (VK-X200), and the maximum height roughness (Rz) was obtained in accordance with JIS B 0601 (2001) .
- the measurement result of the height of an embossed portion is shown in Table 3.
- a visible light transmittance was measured at 20°C using a spectrometer U-4100 (manufactured by Hitachi High-Tech Science Corporation) in accordance with JIS R 3106.
- the measurement result of the visible light transmittance is shown in Table 3.
- An average transmittance of infrared light in the wavelength range of 800 to 1,100 nm was measured at 20°C using a spectrometer U-4100.
- the measurement result of the average transmittance of infrared light in the wavelength range of 800 to 1,100 nm is shown in Table 3.
- a weathering test was performed for the formed laminated glass by exposure for 200 hours under the conditions that the irradiance was 180 W/m 2 , the black panel temperature was 60°C, and the relative humidity was 50% using a weathering testing machine (Super Xenon Weather Meter SX75, manufactured by Suga Test Instruments Co., Ltd.).
- the color difference of the laminated glass was measured using a color-difference meter (SM-T, manufactured by Suga Test Instruments Co., Ltd.) before and after the weathering test.
- SM-T color-difference meter
- a value obtained by subtracting the color difference of the laminated glass after the weathering test from the color difference of the laminated glass before the weathering test was determined as the change in the color difference ⁇ E*ab.
- the measurement result of the change in the color difference ⁇ E*ab is shown in Table 3.
- the sound transmission loss of the laminated glass was measured by a method defined in ASTM E 90-09 (Standard Test Method for Laboratory Measurement of Airborne Sound Transmission Loss of Building Partitions and Elements). The measurement result of the sound transmission loss is shown in Table 3.
- the haze of the laminated glass was measured in accordance with JIS K 7105.
- the measurement result of the haze of the laminated glass is shown in Table 3.
- An interlayer film for laminated glass and a laminated glass were formed in the same manner as in Example 1 except that instead of blending CWO in the layer A, CWO was blended in the layer B, and the area density thereof in the layer B was set to 0.28 g/m 2 , and the evaluation of the respective physical properties was performed.
- the composition and the thickness of the interlayer film for laminated glass are shown in Table 2, and the evaluation result of the respective physical properties is shown in Table 3.
- An interlayer film for laminated glass and a laminated glass were formed in the same manner as in Example 1 except that in the layer B, instead of using 100 parts by mass of PVB-1, a mixture of 100 parts by mass of PVB-2 (shown in Table 1) and 15 parts by mass of a polyester polyol was used, and the evaluation of the respective physical properties was performed.
- the composition and the thickness of the interlayer film for laminated glass are shown in Table 2, and the evaluation results of the respective physical properties are shown in Table 3.
- the polyester polyol Kuraray Polyol P-510 (poly[(3-methyl-1,5-pentanediol)-alt-(adipic acid)], manufactured by Kuraray Co., Ltd.) was used.
- An interlayer film for laminated glass and a laminated glass were formed in the same manner as in Example 1 except that in the layer B, instead of using 100 parts by mass of PVB-1, a mixture of 100 parts by mass of PVB-2 and 37 parts by mass of a polyester polyol was used, and the evaluation of the respective physical properties was performed.
- the composition and the thickness of the interlayer film for laminated glass are shown in Table 2, and the evaluation results of the respective physical properties are shown in Table 3.
- TPE-2 polystyrene-polyisoprene-polystyrene triblock copolymer
- An interlayer film for laminated glass and a laminated glass were formed in the same manner as in Example 1 except that as the main component of the layer A, TPE-3 was used in place of TPE-1, the thickness of the layer A was set to 250 ⁇ m, and the thickness of the layer B was set to 255 ⁇ m, and the evaluation of the respective physical properties was performed.
- the composition and the thickness of the interlayer film for laminated glass are shown in Table 2, and the evaluation results of the respective physical properties are shown in Table 3.
- An interlayer film for laminated glass and a laminated glass were formed in the same manner as in Example 1 except that in the layer A, instead of setting the area density of CWO to 0.25 g/m 2 , the area density of CWO was set to 0.16 g/m 2 , and further, ITO (tin-doped indium oxide, manufactured by Mitsubishi Materials Electronic Chemicals Co. , Ltd.) was added and the area density of ITO was set to 0.75 g/m 2 , and the evaluation of the respective physical properties was performed.
- the composition and the thickness of the interlayer film for laminated glass are shown in Table 4, and the evaluation results of the respective physical properties are shown in Table 5.
- An interlayer film for laminated glass and a laminated glass were formed in the same manner as in Example 1 except that in the layer A, ITO was used in place of CWO, and the area density of ITO was set to 1.50 g/m 2 , and the evaluation of the respective physical properties was performed.
- the composition and the thickness of the interlayer film for laminated glass are shown in Table 4, and the evaluation results of the respective physical properties are shown in Table 5.
- An interlayer film for laminated glass and a laminated glass were formed in the same manner as in Example 7 except that in the layer A, the area density of ITO was set to 4.70 g/m 2 , and the evaluation of the respective physical properties was performed.
- the composition and the thickness of the interlayer film for laminated glass are shown in Table 4, and the evaluation results of the respective physical properties are shown in Table 5.
- Example 6 Example 7
- Additive Heat shielding material Type CWO/ITO ITO ITO Layer A Area density (g/m 2 ) 0.16/0.75 1.50 4.70
- An interlayer film for laminated glass and a laminated glass were formed in the same manner as in Example 1 except that as the main component of the layer A, TPE-2 was used in place of TPE-1, the thickness of the layer A was set to 330 ⁇ m, the thickness of the layer B was set to 215 ⁇ m, and the UV absorber was not used in the layer B, and the evaluation of the respective physical properties was performed.
- the composition and the thickness of the interlayer film for laminated glass are shown in Table 6, and the evaluation results of the respective physical properties are shown in Table 7.
- An interlayer film for laminated glass and a laminated glass were formed in the same manner as in Example 2 except that as the main component of the layer A, TPE-2 was used in place of TPE-1, the thickness of the layer A was set to 330 ⁇ m, and the thickness of the layer B was set to 215 ⁇ m, and the evaluation of the respective physical properties was performed.
- the composition and the thickness of the interlayer film for laminated glass are shown in Table 6, and the evaluation results of the respective physical properties are shown in Table 7.
- An interlayer film for laminated glass and a laminated glass were formed in the same manner as in Example 1 except that in the hydrogenation treatment of the block copolymer used in the layer A, the supply amount of hydrogen was set to 50 mol% with respect to the amount of double bonds in the block copolymer so that a hydrogenated product in which the amount of residual double bonds is 50 mol% (hereinafter referred to as "TPE-4") was formed, and the UV absorber was not used in the layer B, and the evaluation of the respective physical properties was performed.
- TPE-4 hydrogenated product in which the amount of residual double bonds is 50 mol%
- An interlayer film for laminated glass and a laminated glass were formed in the same manner as in Example 1 except that in the hydrogenation treatment of the block copolymer used in the layer A, instead of setting the hydrogen pressure to 1 MPa, the hydrogen pressure was set to 10 MPa so that a hydrogenated product in which the amount of residual double bonds is 1 mol% (hereinafter referred to as "TPE-5") was formed, and the UV absorber was not used in the layer B, and the evaluation of the respective physical properties was performed.
- TPE-5 a hydrogenated product in which the amount of residual double bonds is 1 mol%
- An interlayer film for laminated glass and a laminated glass were formed in the same manner as in Example 1 except that in the layer A, in place of 100 parts by mass of TPE-1, a mixture of 100 parts by mass of PVB-3 (shown in Table 1) and 50 parts by mass of 3G8 (triethylene glycol di-2-ethylhexanoate) was used, and the heat shielding material, the UV absorber, the antioxidant, the light stabilizer, and the adhesive strength adjusting agent were not used, and in the layer B, a mixture of 100 parts by mass of PVB-2 and 38 parts by mass of 3G8 was used, and the UV absorber was not used, and the evaluation of the respective physical properties was performed.
- the composition and the thickness of the interlayer film for laminated glass are shown in Table 6, and the evaluation results of the respective physical properties are shown in Table 7.
- An interlayer film for laminated glass and a laminated glass were formed in the same manner as in Example 1 except that in the layer A, in place of 100 parts by mass of TPE-1, a mixture of 100 parts by mass of PVB-3 and 50 parts by mass of 3G8 (triethylene glycol di-2-ethylhexanoate) was used, and the adhesive strength adjusting agent was not used, and in the layer B, in place of 100 parts by mass of PVB-1, a mixture of 100 parts by mass of PVB-2 (shown in Table 1) and 38 parts by mass of 3G8 was used, and the evaluation of the respective physical properties was performed.
- the composition and the thickness of the interlayer film for laminated glass are shown in Table 6, and the evaluation results of the respective physical properties are shown in Table 7.
- An interlayer film for laminated glass and a laminated glass were formed in the same manner as in Example 1 except that in the layer A, the adhesive strength adjusting agent was not used, and in the layer B, instead of using PVB-1, an ionomer (SentryGlas (R) interlayer, manufactured by DuPont, Inc.) was used, and the evaluation of the respective physical properties was performed.
- the composition and the thickness of the interlayer film for laminated glass are shown in Table 8, and the evaluation results of the respective physical properties are shown in Table 9.
- An interlayer film for laminated glass and a laminated glass were formed in the same manner as in Example 5 except that in the layer A, the adhesive strength adjusting agent was not used, and in the layer B, instead of using PVB-1, an ionomer was used, and the thickness of the layer A was set to 160 ⁇ m, and the thickness of the layer B was set to 300 ⁇ m, and the evaluation of the respective physical properties was performed.
- the composition and the thickness of the interlayer film for laminated glass are shown in Table 8, and the evaluation results of the respective physical properties are shown in Table 9.
- TPE-1 and TPE-2 were melt-kneaded at 200°C at a mass ratio of 1:3, whereby TPE-6 was obtained. Then, an interlayer film for laminated glass and a laminated glass were formed in the same manner as in Example 1 except that in the layer A, TPE-6 was used in place of TPE-1, and the adhesive strength adjusting agent was not used, and in the layer B, an ionomer was used in place of PVB-1, and the thickness of the layer A was set to 220 ⁇ m, and the thickness of the layer B was set to 270 ⁇ m, and the evaluation of the respective physical properties was performed.
- the composition and the thickness of the interlayer film for laminated glass are shown in Table 8, and the evaluation results of the respective physical properties are shown in Table 9.
- An interlayer film for laminated glass and a laminated glass were formed in the same manner as in Example 15 except that instead of blending CWO in the layer A, CWO was blended in the layer B, and the area density thereof in the layer B was set to 0.28 g/m 2 , and the evaluation of the respective physical properties was performed.
- the composition and the thickness of the interlayer film for laminated glass are shown in Table 8, and the evaluation results of the respective physical properties are shown in Table 9.
- An interlayer film for laminated glass and a laminated glass were formed in the same manner as in Example 15 except that as the main component of the layer A, TPE-2 was used in place of TPE-6, the thickness of the layer A was set to 330 ⁇ m, and the thickness of the layer B was set to 215 ⁇ m, and the evaluation of the respective physical properties was performed.
- the composition and the thickness of the interlayer film for laminated glass are shown in Table 8, and the evaluation results of the respective physical properties are shown in Table 9.
- Example 14 Example 15
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KR101936461B1 (ko) * | 2016-07-29 | 2019-01-08 | 현대자동차주식회사 | 합판 유리용 수지 필름, 이를 포함하는 합판 유리 및 이를 포함하는 자동차 |
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EP3827979A1 (de) * | 2019-11-29 | 2021-06-02 | Chang Chun Petrochemical Co., Ltd. | Polymerfilm und verwendungen davon |
US11136441B2 (en) | 2019-11-29 | 2021-10-05 | Chang Chun Petrochemical Co., Ltd. | Polymer film and uses of the same |
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